Laser-induced desorption mass spectrometry techniques

Fast-atom bombardment mass spectrometry (FAB-MS) has been applied to the identification of diterpenoid compounds and their oxidation products. Similarly, laser-induced desorption mass spectrometric (LDMS) techniques have been applied to the identification of natural and synthetic organic pigments in microscopic paint samples prepared as cross sections [60]. 

Secondary-ion mass spectrometry (SIMS) of a thin layer of nucleic acid bases deposited on a silver foil under bombardment with Ar ions at 3 kV gives intense pseudomolecular ions [M H] but practically no simple bond cleavage fragments. Another new technique is that of (pulsed) laser induced desorption (LD). When applied to nucleotide bases such as cytosine or adenine (266 nm, quadruplet neodymium laser or 347 nm, ruby laser) the technique has good detection limits, particularly for ions with a short lifetime (up to 100 nsec). The technique makes use of a time-of-flight instrument and is utilized in both modes, positive (PI) and negative ions (NI). Both bases exhibit an intense [BH]" ion. These results are similar to those obtained by Cf plasma desorption (PD). 

Chapter 7, titled Interfacing TLC with Laser-Based Ambient Mass Spectrometry, provides an overview of mass spectrometric techniques that can be coupled with TLC under the most convenient working conditions, that is, at room temperature and atmospheric pressure. The authors introduce readers to electrospray laser desorption ionization (ELDI), plasma-assisted multiwavelength laser desorption/ionization (PAMLDI), laser desorption atmospheric pressure chemical ionization (LD-APCI), laser desorption-dual electrospray and atmospheric pressure chemical ionization I (LD - ESI-I-APCI), laser-induced acoustic desorption electrospray ionization (LIAD-ESI), and laser-induced acoustic desorption-dielectric barrier discharge ionization (LIAD-DBDI). Chapters 6 and 7 are largely complementary because in the former one, main attention is paid to practical applications of a wide number of... 

Other techniques that have been used to determine polycyclic aromatic hydrocarbons in soil extracts include ELISA field screening [86], micellar elec-tr okinetic capillary chromatography [ 87], supersonic jet laser-induced fluorescence [88,89], fluorescence quenching [90], thermal desorption gas chromatography-mass spectrometry [81,90,100], microwave-assisted extraction [91], thermal desorption [92], immunochemical methods [93,94], electrophoresis [96], thin layer chromatography [95], and pyrolysis gas chromatography [35]. 

A number of less commonly used analytical techniques are available for determining PAHs. These include synchronous luminescence spectroscopy (SLS), resonant (R)/nonresonant (NR)-synchronous scan luminescence (SSL) spectrometry, room temperature phosphorescence (RTP), ultraviolet-resonance Raman spectroscopy (UV-RRS), x-ray excited optical luminescence spectroscopy (XEOL), laser-induced molecular fluorescence (LIMP), supersonic jet/laser induced fluorescence (SSJ/LIF), low- temperature fluorescence spectroscopy (LTFS), high-resolution low-temperature spectrofluorometry, low-temperature molecular luminescence spectrometry (LT-MLS), and supersonic jet spectroscopy/capillary supercritical fluid chromatography (SJS/SFC) Asher 1984 Garrigues and Ewald 1987 Goates et al. 1989 Jones et al. 1988 Lai et al. 1990 Lamotte et al. 1985 Lin et al. 1991 Popl et al. 1975 Richardson and Ando 1977 Saber et al. 1991 Vo-Dinh et al. 1984 Vo- Dinh and Abbott 1984 Vo-Dinh 1981 Woo et al. 1980). More recent methods for the determination of PAHs in environmental samples include GC-MS with stable isotope dilution calibration (Bushby et al. 1993), capillary electrophoresis with UV-laser excited fluorescence detection (Nie et al. 1993), and laser desorption laser photoionization time-of-flight mass spectrometry of direct determination of PAH in solid waste matrices (Dale et al. 1993). 

Then, within a short period, both MALDI (matrix-assisted laser desorption ionization) and electrospray ionization were introduced and found widespread use in biomolecular mass spectrometry. As noted earlier, Koichi Tanaka (MALDI) and John Fenn (electrospray ionization) were awarded the 2002 Nobel Prize in Chemistry for these innovations. Both MALDI and electrospray ionization are considered to be soft ionization techniques that induce little, if any, molecular fragmentation. 

An absolute method for molecular weight determination is matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF) (Kona et al., 2005 Creel, 1993 Nielsen, 1999 Cho et al., 2001). The sample is dispersed in a UV-absorbing matrix (e.g., trans -cinnamic acid or 2,5-dihydroxybennzoic acid). Irradiation with a UV laser induces evaporation of ionized polymer chains, which are then detected using TOF. The technique requires relatively narrow MWD samples. Alternative ionization methods have been employed, such as electrospray ionization mass spectrometry (ESI-MS), which may have advantages for certain polymer end groups (Vana et al., 2002). IFFF and MALDI-TOF can be coupled to analyze polydisperse samples and polymer mixtures (Kassalainen and Williams, 2003). 

Soft ionization MS techniques [9] like electrospray ionization (ESI) and soft laser desorption, often known as matrix-assisted laser desorption/ioniza-tion (MALDI), facilitated the polymer analyses over the last years. The advantage of the soft ionization techniques is the transformation of dissolved liquid or solid sample into the gas phase, where no change in the molecular composition/structure of the sample will be induced, while hard ionization in mass spectrometry (e.g., electron ionization (El) or fast atom bombardment (FAB)) preferentially destroys the chemical and molecular structure into fragments prior to the detection of the molar mass fragments of the sample by mass spectrometry. 

Laser-induced acoustic desorption-electrospray ionization mass spectrometry (LlAD-ESl/MS) is a technique combining an electrospray and a pulsed laser beam to characterize solid and liquid samples with minimal sample preparation [48]. Although the instrumental setup of LIAD-ESl is similar to that of ELDl, the laser intensity required for LIAD (i.e., 10 W/cm ) is higher than that for ELDl, and the desorption mechanism of LIAD is also different from that of LD. In LIAD, the sample is not desorbed by direct laser irradiation, but by acoustic and shock waves induced by the laser irradiation. A pulsed laser beam with a flux energy of several mJ is used to irradiate the rear of a thin metal foil (e.g., AL Ti, Cu, and Ta 5-25 pm thickness) to generate acoustic and shock waves [48-50]. These laser-induced... 

Impurity inclusions and surface defects are a cause of many difficulties to the polymer producer and user. Equipment used for studying these phenomena discussed in Chapter 4 include electron microprobe x-ray emission/spectroscopy, NMR micro-imaging, various forms of surface infrared spectroscopy, e.g., diffusion reflection FTIR, ATR, also photoacoustic spectroscopy and x-ray diffraction - infrared microscopy of individual polymer fibres. Newer techniques such as scanning electron microscopy (SECM), transmission electron microscopy, time of flight secondary ion mass spectrometry (TOFSIMS), laser induced photoelectron ionisation with laser desorption, atomic force microscopy and microthermal analysis are discussed. 

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