INSTRUMENTATION OF NMR

MAGNETS: Magnet is used to supply the principle part of the field, which determines the frequency of any nucleus. The stronger the magnetic field, the better the line separation of chemically shifted nuclei on the frequency scale.

 FEATURES: It should give homogeneous magnetic field ie; the strength and direction of the magnetic field should be constant over longer periods. The strength of the field should be very high at least 20,000 gauss. If the magnetic field is not homogenous the nuclei in the different part of sample process with different frequencies there by producing broad signals.

 MAGNETIC COILS:
It is not easy or convenient to vary the magnetic field of large stable magnets, however this problem can be overcome by superimposing a small variable magnetic field on the main field. Using a pair of Hemoltz coils on the pole faces of the permanent magnet. These coils induce a magnetic field that can be varied by varying the current flowing through them.

 THE PROBE UNIT

It is a sensing element of the spectrophotometer system. It is inserted between the pole faces of the magnet in X-Y plane of the magnet air gap an adjustable probe holder. So the sample in NMR experiment experiences the combined effect of two magnetic fields. The probe contains a sample holder, sweep source and detector coils, with the reference cell. The detector and receiver coils are orientated at 90 to each other. The sample probe rotates the sample tube at a 30-40 revolutions on the longitudinal axis.

THE RADIOFREQUENCY GENERATOR:

Using an RF oscillator required to induce transition in the nuclei of the sample from the ground state to excited states creates the radio frequency radiation. To achieve the maximum interaction of the RFradiation with the sample, the coil of oscillator is wound around the sample container. The RF coil is installed perpendicular (90) to the applied magnetic field and transmits radio waves of fixed frequency such as 60,100,200 or 300 MHz to a small coil that energies the sample in the probe. This is done so that the applied field should not change the effective magnetic field in the process of irradiation. 1. 2. 3. 4. 5. 6. Oscillators used in NMR spectrophotometers are, Robinsons valve version oscillator Robinsons field effect transistor version oscillator. W.D.Knights oscillator. Tunable low temp oscillator New sensitive marginal oscillator P.K.W oscillator etc.,

SWEEP GENERATOR:

Large magnet as well as the RF oscillators both produces fixed fields. Hence a sweep generator is installed to supply variables in either of these two fields . The precession frequency of nucleus should equal to frequency of applied Rf field .If the applied magnetic field (H0) is constant the precession frequency is fixed in order to bring about resonance, the frequency of Rf field should change so that it becomes to resonance frequency (because of frequency sweep method )

RADIO FREQUENCY RECIEVER OR DETECTOR: A few turns of wire is wound around the sample tube lightly. This receiver coil is perpendicular to both the external magnetic and radiofrequency transmitter coil. When RF radiation is passed through the magnetised sample resonance occurs which cause the current voltage across the coil to drop. This electrical signal is small and is usually amplified before recording.

Classification of the NMR spectrophotometers

Conventional/Continuous NMR spectrophotometer Pulsed Fourier transform NMR spectrophotometer

The continuous wave (CW) instrument. WORKING The sample (0.5 mg) is dissolved in a solvent containing no interfering protons usually CCl4 or CDCl3 0.5 ml and a small amount of TMS is added to serve as an internal reference. The sample cell is rotated around its axis to ensure that all parts of the solution experience a relatively uniform magnetic field. This increases the resolution of the spectrum. Also in the magnetic gap, the radio frequency oscillator coil is installed perpendicular (90) to the applied magnetic field. This coil supplies the electromagnetic energy used to change the spin orientations of the protons. Perpendicular to the RF oscillator coil is the detector coil. as the magnetic field strength is increased ,the precessional frequencies of all the protons increases.

 As the magnetic field strength is increased linearly, a pen travel from left to the right on a recording chart. as each chemically distinct type of proton comes into resonance, it is record as a peak on the chart. The peak at delta=0 ppm is due to the internal reference compound TMS. Since highly shielded protons process more slowly than relatively unshielded protons. Hence highly shielded protons appear to the right of the chart, and less shielded or dishelded protons appear to the left. The region of the chart to the left is sometimes said to be downfield and that to the right, up field. Instruments which vary the magnetic field in a continuos fashion scanning from the downfield end to up field end of the spectrum, are called continuous wave instruments. The chemical shifts of the peaks in this spectrum are calculated from the frequency differences from the TMS, this type of spectrum is said to be frequency domain spectrum. Peaks generated by a CW instrument have ringing. Ringing occurs because the excited nuclei do not have time to relax back to their equilibrium state before the field. And pen, of the instrument have advanced to a new position. Ringing is most noticeable when a peak is a sharp Singlet.

The pulsed Fourier Transform (FT ) instrument

The continuous wave type of NMR spectrometer operates by exciting the nuclei of the isotope under observation one type at a time. An alternative approach, common to modern, sophisticated instrument , is to use a powerful but short burst of energy called a pulse that excites all of the magnetic nuclei in the molecule simultaneously and all the signals are collected at the same time with a computer.

 When the pulse is discontinued the excited nuclei begin to lose their excitation energy and return to the original state or relax. As each excited nucleus relaxes it emits EMR. Since the molecule contains many different nuclei many different frequencies of EMR are emitted simultaneously. This emission is called a freeinduction decay (FID) signal. We usually extract individual frequencies due to different nuclei by using a computer and a mathematical method called a Fourier-transform analysis. The Fourier transform breaks the FID into its separate sine or cosine wave components. One can calculate the frequency of this wave from its measured wavelength.

Components of FT-NMR FT A simplified form of the block diagram showing the instrument components of a typical Fourier transform nmr spectrometer. The central component of the instrument is a highly stable magnet in which the sample is placed. The sample is surrounded by the transmitter/receiver coil. A crystal controlled frequency synthesizer having an output frequency of Vc produces radio-frequency radiation. This signal passes into a pulsar switch and power amplifier, which creates an intense and reproducible pulse of RF current in the transmitter coil. The resulting fid signal is picked up by the same coil which now serves a as receiver. The signal is then amplified and transmitted to a phase sensitive detector. The detector circuitry produced the difference between the nuclear signals Vn and the crystal oscillator output Vc which leads to the low frequency time-domain signal as shown in the fig. This signal is digitalized and collected in the memory of the computer for analysis by a Fourier transform program and other data analysis software. The output from this program is plotted giving a frequency domain spectrum.

Advantages of FT NMR

FT-NMR is more sensitive and it can measure weaker signals. The pulsed FT-NMR is much faster (seconds instead of min) as compared to continuous wave NMR. FT-NMR can be obtained with less than 0.5 mg of compound. This is important in the biological chemistry, where only g quantities of the material may be available. The FT method also gives improved spectra for sparingly soluble compounds. The signals standout clearly with almost no electronic background noise.

References:
1. Willard H.H, Meritt Jr.L.L, Dean J.A, Settle Jr.F.A, Instrumental methods of analysis, 7th edition.427-438. 2. Donald.L.P, Lampman G.M, George S.K, Introduction to spectroscopy, 3rd edition.113-116. 3. Skoog D.A, Holler F.J, Nieman T.A, Principles of instrumental analysis, 5th edition.470-473. 4. Silverstein R.M, Webmaster F.A, Spectrometric identification of organic compounds, 6th edition.148-150.