Signal intensity spectra

Figure B2.1.3 Output of a self-mode-locked titanium-sapphire oscillator (a) non-collinear intensity autocorrelation signal, obtained with a 100 pm p-barium borate nonlinear crystal (b) intensity spectrum.

In Laser Ionization Mass Spectrometry (LIMS, also LAMMA, LAMMS, and LIMA), a vacuum-compatible solid sample is irradiated with short pulses ("10 ns) of ultraviolet laser light. The laser pulse vaporizes a microvolume of material, and a fraction of the vaporized species are ionized and accelerated into a time-of-flight mass spectrometer which measures the signal intensity of the mass-separated ions. The instrument acquires a complete mass spectrum, typically covering the range 0— 250 atomic mass units (amu), with each laser pulse. A survey analysis of the material is performed in this way. The relative intensities of the signals can be converted to concentrations with the use of appropriate standards, and quantitative or semi-quantitative analyses are possible with the use of such standards. 

Several features of ISS quantitative analysis should be noted. First of all, the relative sensitivities for the elements increase monotonically with mass. Essentially none of the other surface spectroscopies exhibit this simplicity. Because of this simple relationship, it is possible to mathematically manipulate the entire ISS spectrum such that the signal intensity is a direct quantitative representation of the surface. This is illustrated in Figure 5, which shows a depth profile of clean electrical connector pins. Atomic concentration can be read roughly as atomic percent direcdy from the approximate scale at the left. 

Figure 2.36 A shows a typical low-loss spectrum taken from boron nitride (BN). The structure of BN is similar to that of graphite, i. e. sp -hybridized carbon. For this reason the low-loss features are quite similar and comprise a distinct plasmon peak at approximately 27 eV attributed to collective excitations of both n and a electrons, whereas the small peak at 7 eV comes from n electrons only. Besides the original spectrum the zero-loss peak and the low-loss part derived by deconvolution are also drawn. By calculating the ratio of the signal intensities hot and Iq a relative specimen thickness t/2 pi of approximately unity was found. Owing to this specimen thickness there is slight indication of a second plasmon.

E/Z ratios were determined from relative signal intensities in the F NMR spectrum. 

The matrix obtained after the F Fourier transformation and rearrangement of the data set contains a number of spectra. If we look down the columns of these spectra parallel to h, we can see the variation of signal intensities with different evolution periods. Subdivision of the data matrix parallel to gives columns of data containing both the real and the imaginary parts of each spectrum. An equal number of zeros is now added and the data sets subjected to Fourier transformation along I,. This Fourier transformation may be either a Redfield transform, if the h data are acquired alternately (as on the Bruker instruments), or a complex Fourier transform, if the <2 data are collected as simultaneous A and B quadrature pairs (as on the Varian instruments). Window multiplication for may be with the same function as that employed for (e.g., in COSY), or it may be with a different function (e.g., in 2D /-resolved or heteronuclear-shift-correlation experiments). 

The addition of ethanolamine to the enzyme-coenzyme complex resulted in greater than 90% loss in signal intensity. When the substrate supply was exhausted, the original ESR spectrum reappeared slowly but did not regain its full intensity after 30 minutes. Under the experimental... 

So far we have dealt with the chemical shift and coupling constant information in the proton spectrum. What we have not considered is the third important parameter, the signal intensity this forms the vertical axis of the spectrum, but is not scaled since we do not use intensity units. 

It is in fact quite simple to record a carbon-13 spectrum with the broadband decoupling switched off. Such a procedure has the disadvantage that the gain in signal intensity due to the NOE is lost, so that measurement times are very long. 

Resolvable modulation is detected on a three-pulse echo decay spectrum of predeuterated 3-carotene radical (Gao et al. 2005) as a function of delay time, T. The resulting modulation is known as ESEEM. Resolvable modulation will not be detected for nondeuterated P-carotene radical since the proton frequency is six times larger. The modulation signal intensity is proportional to the square root of phase sensitive detection and interfering two-pulse echoes and suppressed by phase-cycling technique (Gao et al. 2005). Analysis of the ESEEM spectrum yields the distance from the radical to the D nucleus, a the deuterium coupling constant, and the number of equivalent interacting nuclei (D). The details related to the analysis of the ESEEM spectrum are presented in Gao et al. 2005. 

Of course, it is quite easy to solve the bandwidth needs of proton spectra - they only have a spread over about 20 ppm (8 kHz at 400 MHz). Things get a bit more difficult with nuclei such as 13C where we need to cover up to 250 ppm (25 kHz) spread of signals and we do notice some falloff of signal intensity at the edge of the spectrum. This is not normally a problem as we seldom quantify by 13C NMR. However, it can be a problem for some pulse sequences that require all nuclei to experience 90°... 

Phase The representation of an NMR signal with respect to the distribution of its intensity. We aim to produce a pure absorption spectrum (one where all the signal intensity is positive). 

---