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NMR Data Acquisition The process of data acquisition results in an ...

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<strong>of</strong> nucleus <strong>in</strong> the molecule (e.g., the CH 3 , CH 2 <strong>an</strong>d OH protons <strong>in</strong> eth<strong>an</strong>ol) has its own reson<strong>an</strong>t<br />

frequency, so the FID consists <strong>of</strong> a superposition <strong>of</strong> a number <strong>of</strong> pure frequencies, correspond<strong>in</strong>g<br />

to a number <strong>of</strong> peaks <strong>in</strong> the spectrum. All <strong>of</strong> the <strong>in</strong>formation <strong>of</strong> the <strong>NMR</strong> spectrum is conta<strong>in</strong>ed<br />

<strong>in</strong> the FID, <strong>an</strong>d a large part <strong>of</strong> the spectrometer is devoted to amplify<strong>in</strong>g, record<strong>in</strong>g <strong>an</strong>d <strong>an</strong>alyz<strong>in</strong>g<br />

this signal.<br />

4. <strong>The</strong> Receiver amplifies the radio frequency FID signal com<strong>in</strong>g from the probe,<br />

converts it to <strong>an</strong> audio frequency signal by subtract<strong>in</strong>g out the radio frequency at the center <strong>of</strong> the<br />

spectral w<strong>in</strong>dow, amplifies it some more, <strong>an</strong>d then converts it to a list <strong>of</strong> numbers. <strong>The</strong> total<br />

amplification given to the FID <strong>in</strong> the receiver is called the Receiver Ga<strong>in</strong> (Vari<strong>an</strong>: GAIN or<br />

Bruker: RG). <strong>The</strong> <strong>in</strong>tensity <strong>of</strong> the FID signal <strong>in</strong>duced <strong>in</strong> the probe coil depends on the sample<br />

concentration, so the amount <strong>of</strong> ga<strong>in</strong> or amplification <strong>in</strong> the receiver must be adjusted for each<br />

new sample. <strong>The</strong> audio signal com<strong>in</strong>g <strong>in</strong>to the digitization stage (the <strong>an</strong>alog-to-digital converter<br />

or ADC) should ideally be <strong>of</strong> the same magnitude for all samples, regardless <strong>of</strong> concentration.<br />

<strong>The</strong> ADC has a maximum r<strong>an</strong>ge <strong>of</strong> <strong>in</strong>teger values that it c<strong>an</strong> give to the signal as it comes <strong>in</strong>,<br />

usually -32,767 to 32,768 (Fig. 8). If the signal is amplified too little before digitization,<br />

the<br />

Figure 8. <strong>The</strong> ADC ("digitizer") c<strong>an</strong> be<br />

viewed as a ladder <strong>of</strong> possible numerical<br />

values. In the figure <strong>in</strong>teger values <strong>of</strong> -<br />

13 to +13 are shown, but <strong>in</strong> reality the<br />

r<strong>an</strong>ge is usually more like -32767 to<br />

+32768. If the ga<strong>in</strong> is set too high, the<br />

first portion <strong>of</strong> the FID has <strong>an</strong> <strong>an</strong>alog<br />

voltage higher th<strong>an</strong> the maximum <strong>of</strong> the<br />

digitizer, so these values are "clipped" at<br />

the maximum value. This will lead to<br />

large basel<strong>in</strong>e rolls <strong>in</strong> the spectrum. <strong>The</strong><br />

optimal ga<strong>in</strong> just fills the digitizer with<br />

signal without exceed<strong>in</strong>g the limits. If<br />

the ga<strong>in</strong> is set too low, the shape <strong>of</strong> the<br />

signal is lost <strong>an</strong>d a “blocky”<br />

representation <strong>results</strong>. This reduces<br />

signal-to-noise ratio <strong>an</strong>d dynamic r<strong>an</strong>ge.<br />

numbers will get "gra<strong>in</strong>y": they<br />

might r<strong>an</strong>ge from -7 to +8 with<br />

only 16 possible values. In this<br />

case it would be very difficult to<br />

f<strong>in</strong>d a small peak <strong>in</strong> the spectrum<br />

<strong>in</strong> the presence <strong>of</strong> big ones (<strong>in</strong><br />

f<strong>an</strong>cy l<strong>in</strong>go, this is called a<br />

"dynamic r<strong>an</strong>ge" limitation). If, on the other h<strong>an</strong>d, if the signal is amplified too much, it might<br />

exceed the digitizer limits <strong>an</strong>d get truncated or "cut <strong>of</strong>f". For example, a signal which would give<br />

a value <strong>of</strong> 52,314 would be read as 32,768 because the digitizer c<strong>an</strong>'t respond to <strong>an</strong>y larger value.<br />

This cutt<strong>in</strong>g <strong>of</strong>f or "clipp<strong>in</strong>g" has very drastic effects on the spectrum: the basel<strong>in</strong>e gets huge<br />

23

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