NUCLEAR MAGNETIC RESONANCE

the most powerful tool for determining the structure of organic compounds it is called nuclear for the instrument works on stimulating the nuclei of the atoms to absorb radio waves. relies on the ability of atomic nuclei to behave like a small magnet and to align with external magnetic field.

The frequency of radiation necessary for adsorption of energy depends on three things: 1) characteristic of the type of nucleus (e.g., 1H or 13C) 2) chemical environment of the nucleus 3) spatial location in the magnetic field

- resultant of the spin and orbital angular momenta of the neutrons and protons that compose the nucleus - characterized by a quantum number I, which may be integral, half-integral or 0 The magnetic quantum number mI has values of I, -I+1, ..+I

1. A nucleus with an even mass A and even charge Z -> nuclear spin I is zero Ex: 12C, 16O, 32S -> No NMR signal 2. A nucleus with an even mass A and odd charge Z -> integer value I Ex: 2H, 10B, 14N -> NMR detectable 3. A nucleus with odd mass A -> I=n/2, where n is an odd integer Ex: 1H, 13C, 15N, 31P ->NMR detectab

NUCLEUS
1H 2H 7Li 13C 14N 15N 17O

% ABUNDANCE 99.99 0.01 92.5 1.11 99.6 0.4 0.04

SPIN I 1/2 1 3/2 1 5/2

gN 5.585 0.857 2.171 1.405 0.403 -0.567 -0.757

The magnitude of the nuclear spin angular momentum (I) is I=[I(I+1)]h The z component of nuclear spin (Iz) is given by Iz = mih where mi = -I, -I+1,... I-1, I total of (2I+1) The magnetic dipole moment therefore of the nucleus ( n) is:
n

= gn

NI

Where: gn=nuclear g factor = 5.051 x 10 -27 JT

Boltzmann distribution
Quantum mechanics tells us that, for net absorption of radiation to occur, there must be more particles in the lower-energy state than in the higher one. If no net absorption is possible, a condition called saturation occurs. The rate of absorption is proportional to the number of nuclei in lower state (Nl); rate of emission is proportional to the number in upper state (Nu).

Nu = e-E/KT = e-gn Nl = 1-gn

NB/Kt

NB

kT It follows that Nl Nu = gn NB Nl+Nu 2kT

Sample Problem
What is the ratio of the number of proton spins in the lower state to the number in the higher state in the magnetic field of 1 T at room temperature? What is the excess population in the lower state? Nl/Nu = 1 + (gn NB) = 1 + [(5.585)(5.05x10-27 J T-1)(1T)]/[(1.38x10-23J K1)
(298K)]

= 1 + 6.86x10-6 (N1 - Nu)/(N1 + Nu) = 3.43 x 10-6

Deriving the Boltzmann equation:

Taking the ideal gas equation PV = nRT Rearranging gives: PV = (nNa)(R/NA)T PV = (nNA)(kT) Rearranging again gives: PV = (nNA/V)(kT)

- A nucleus with a magnetic moment may interact with other nuclei spins resulting in mutual splitting of NMR signal from each nucleus into multiplets - Splitting of resonances into peaks
Reference: http://bouman.che m.georgetown.edu/nmr/scalar/scalar.htme

A nuclear magnetic moment will precess about the axis of an externally applied field at a frequency proportional to the strength of the applied field, Bo. = Bo(rad/s) = Bo/2 Larmor Frequency The direction of motion can be clockwise or counterclockwise and is determined by the sign of . By convention, the field is applied along the z axis of a Cartesian co-ordinate frame.

Derivation of Larmor Frequency Formula

From which is the maximum observable component in any particular allowed direction, and E= energy,
nH n=gn NI

which is the potential

 By substituting the 1st equation to the 2nd, we will get E = -gn NHI The difference in energy, E, between two levels I 1 and I 2 follows: E = E2 E1 = -gn NH(I 2 I 1) But, selection rules limit transitions only to adjacent levels, i.e., I = I 2 I 1 = +- 1. Hence,

But, selection rules limit transitions only to adjacent levels, i.e., I = I 2 I 1 = +- 1. Hence, E = +-gn NH Since E = hv, the frequency which corresponds to a transition is v = E /h = +- gn
NH/h

Chemical Shift
Describes the dependence of nuclear magnetic energy levels on the electronic environment in a molecule. The variations of nuclear magnetic resonance frequencies of the same kind of nucleus, due to variations in the electron distribution

 The study of chemical shifts has produced a large store of information about the chemical bonds and the structure of molecules. the chemical shift is usually indicated by a symbol which is defined in terms of a standard reference.

(Vs  Vr ) v10 H! Vr

 The signal shift is very small, parts per million, but the great precision with which frequencies can be measured permits the determination of chemical shift. The reference material is often tetramethylsilane, Si(CH3)4, abbreviated TMS. Since the signal frequency is related to the shielding by:

 Chemical shift can be expressed by:

It consists of a magnet that can produce a uniform, intense field and the appropriate sources of radio freqeuncy electromagnetic radiation. The magnetic field is provided by a permanent magnet

 a superconducting magnet capable of producing fields of the order of 2T and more is used sample is usually operated at room temperature eventhough a superconducting magnet operates at the temperature liquid helium (4K)

Troubleshooting

Why can't I lock the spectrometer? Locking problems can be caused by incorrectly set lock parameters (Z0, loc power, lock phase, lock gain) and/or by very badly adjusted shims. Make sure that you are using a deuterated solvent and have selected the correct solvent under the setup menu.

Common Reasons for Inability to Lock

Cause No deuterated solvent Shimming is very poor Suspended particles Too concentrated Improperly gauged Lockpower is too low

Solution Use a deuterated solvent No deuterium signal to lock on. like CDCl3. The signal is so broad that it is not well Type fixshims to get a good observed. start. This causes line broadening, which Filter your sample. makes the signal intensity weaker. There is little deuterated solvent to get Dilute your sample or use a a lock. Especially problematic when using solvent with more CDCl3. deuteriums (e.g. C6D6). Eject sample and ensure When injected, the sample is not in the that the sample resides coil. between the white lines on the gauge. Increase lockpower to 80% The sample is not receiving enough rf of max before trying to signal to flip the deuterium spins. lock.

Result

 This is usually a result of a failure in the acquisition computer. Look at the ACQUISITION STATUS window and see if the Status is Idle, Acquiring, or Inactive. If it is Acquiring, type aa. If you get the message similar to,'no experiment is active', you will need to reboot the acquisition computer. If it is Inactive, you will need to reboot the acquisition computer.

 If it is Idle, try typing exit. Wait about 1 minute. If you are not exited from the VNMR program, you will need to reboot the acquisition computer.

If rebooting does not work.

How can I control the temperature?

First of all, make sure that the VT gas supply to the probe is correctly connected and adjusted. You may also need to reset the VT controller.

Poor Shimming:
Common Reasons for Poor Shimming

Cause Result No deuterated No deuterium signal to lock on and, thus solvent nothing to shim on. Initial shimming is Your peaks are very broad. poor Suspended This causes line broadening, which makes particles the signal intensity weaker. Concentrated samples can be viscous, Too concentrated which will cause line broadening. When injected, the sample is not properly positioned in the coil and the liquid/air Too little solvent interface is 'seen' by the coil. This will make shimming very difficult. When injected, the sample is not properly Improperly positioned in the coil and the liquid/air gauged interface is 'seen' by the coil. This will make shimming very difficult.

Solution Use a deuterated solvent like CDCl3. Type fixshims to get a good start. Filter your sample. Dilute your sample.

Add more solvent.

Eject sample and ensure that the sample resides between the white lines on the gauge.

The Computer Screen is Blank

My Sample is not Spinning

The VNMR Screen Colors are Terrible

The odd colors for your VNMR interface are usually a result of having too many windows/applications open.

What should I do if I have printing problems?

Nuclear Magnetic Resonance Spectroscopy Applications

CHEMISTRY
DETERMINING THE STRUCTURE OF COMPOUNDS

NUCLEAR MAGNETIC RESONANCE IS EXTREMELY USEFUL FOR ANALYZING SAMPLE NON DESTRUCTIVELY

APPLICATIONS OF NMR IN MEDICINE

 CLINICAL APPLICATION OF PROTON IN DIAGNOSIS BRAIN IMAGING

Distinguishing gray matter & white matter  Imaging posterior fossae, brain stem, spinal cord  Detect demyelinating lesions, tumors, hemorrhages, infarctions