Soft pulse energy

Fig. 14. Schematic of selective excitation and ID exchange spectroscopy, (a) Typical pulse sequence with a soft selective pulse centered at pulsation a>s with a frequency dispersion AcoP <3C Aoj much smaller than the typical linewidth. After an evolution time te smaller or of the order of the spin-lattice relaxation time, a reading sequence of hard pulses that covers uniformly the whole broad line is applied, (b) Effect of a selective excitation on a homogeneously broaden line, (c) Selective frequency labeling of an inhomogeneously broaden line at the irradiation pulsation cos of the first soft pulse. For a soft n pulse, the magnetizations of all the spins that can exchange energy at this pulsation are reversed. By following the difference spectra between the spectra acquired at different evolution times te and the fully relaxed spectrum AS(te) — S(t -> oo) — S(te), limits or evaluation of the correlation time tc of the motion can be achieved.

A schematic of the basic principles of a matrix-assisted laser desorption/ion source is shown in Figure 2.35. By the interaction of a focused laser beam with short pulses and a suitable matrix, the energy of the photons is transferred to the matrix molecules. In MALDI mostly pulsed UV (e.g., nitrogen, X = 337 nm, pulse duration 3-10 ns), but also IR lasers (e.g., Er YAG, X = 2.94 (xm or C02, X = 10.6(xm with a higher pulse duration of up to 600 ns) are used. The MALDI mass spectra obtained during soft ionization by UV and IR lasers are identical. The energy density... 

This desorption ionisation technique leads to weak fragmentation. The analyte is incorporated into a solid organic matrix (such as hydroxybenzoic acid) and the mixture is placed on a sample holder that is irradiated with UV laser pulses (e.g. N2 laser, A = 337 nm, pulse width = 5 ns). The laser energy is absorbed by the matrix and transferred to the analyte, which becomes desorbed and ionised (Fig. 16.18c). Although MALDI is considered to be a soft ionisation technique, a substantial amount of energy is involved. Because the technique involves pulsed ionisation, it is well suited for time-of-flight mass analysis of biomolecules. The analysis of small molecules (M < 500 Da) is limited because the matrix decomposes upon absorption of the laser radiation. However, solid supports such as silicone can be used as the matrix to overcome this disadvantage. 

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