Pulsed ionisation techniques

Detection limits in the lOOfg range can be obtained with a tuneable UV laser working at a wavelength of maximum absorption for the compounds of interest. Continuous supersonic beams require high gas loads and combination with a pulsed ionisation technique (e.g. REMPI) is unfavourable in terms of sensitivity. Pulsed valves are a better approach for a GC-UV-MS interface [1021]. 

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. 

Others groups [71, 72, 73, 74] obtained an improvement of mass accuracy and peak resolution by the use of a delayed extraction system [75]. This system uses a pulsed ion extraction MALDI ionisation technique increasing the accelerating voltage from 0 up to 3 kV in 300 nanoseconds. This technique allowed an increase of peak resolution for cytochrome c (12 kDa) from 350 FWHM obtained in linear mode to 1024 with a continuous ion extraction. 

Glow discharge is essentially a simple and efficient way to generate atoms. Long known for its ability to convert solid samples into gas-phase atoms, GD techniques provide ground-state atoms for atomic absorption or atomic fluorescence, excited-state atoms for atomic emission, and ionised atoms for MS [158], Commercial instrumentation has been developed for all these methods, except for GD-AFS and pulsed mode GD. 

The mass spectrometry analysis was performed by the matrix assisted laser desorption/ionisation time-of-flight (S8-MALDI) technique using a Voyager-DE PRO Biospectrometry Workstation (Applied Biosystems, USA). Radiation pulses of 0.5 ns and 3 Hz frequency from N2 laser operating at 337 nm were used to desorb the species and negative/positive ions formed were detected in reflectron mode. Sulfur used as a matrix material was also dissolved in toluene and mixed with the samples solution prior to deposition onto a target. 

The energy of the 7) state can also be determined for soluble conjugated polymers by the technique of T-T energy transfer (Monkman et al., 2001). When the solvent in a polymer solution is ionised with an intense, pulsed electron beam, charge recombination gives rise to excited solvent molecules in... 

A recently introduced technique for the separation of larger molecules is matrix-assisted faser Resorption-ionisation mass spectrometry (MALDI-MS). Developed by Karas et al. [4, 5] in 1988, it has been successfully used to determine the mass of biomolecules up to 500.000 Da. This method is based on the principle that the dissolved specimen is mixed with a matrix, and then crystallizes. After drying, a laser pulse is directed onto the solid matrix to photo-excite the matrix material,resulting in desorption and soft ionisation of the analyte.The molar mass is then determined by the lime ef ilight (TOF). 

Dorfman and collaborators have recently developped a very promising technique for the production of carbenium ions as transient species in halocarbon sdvents based on the dissociative ionisation of suitable precursors induced by pulse radiolysis of the solvent. While the extremely interesting kinetic results vdiich this group is obtaining will be discussed in Sect. II-G4, it is emphasised here that the fast time response of the apparatus used allows the characterisation of carbenium ions hitherto unobservable because of their excessive reactivity. The ultraviolet absorption spectrum and some reactions of the benzylium ion have been studied for the first time wdth this powerful tool. From the point of view of cationic pdymerisation, the information obtained in this type of work is particularly relevant, since it deals vrith the identification and reactivity of carbenium icais formed in very low concentration in the nght kind of medium. Cation radicals had already been prepared by pulse radiolysis involving nondissociative ionization (electron ejection or transfer), as will be discussed in Sect. II-K. 

Zewail acknowledged early on that he was inspired to work in the dynamics area by amongst others, George Porter s development of fast reaction techniques, viz. Flash Photolysis which is reported elsewhere in this volume. In the early experiments outlined in the present paper, three detection techniques were employed time-correlated single photon counting, with 30-50 ps time resolution streak camera detection of fluorescence, with 10 ps resolution, and multiphoton ionisation with resolution determined by the pulse width of the laser, 1 or 15 ps. 

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