MALDI Ionisation

Hsiao et al. [11] have studied the use of MALDI ionisation for the detection of antioxidants and hindered amine light stabilisers (HALS) in polyethylene extracts. Using 2,5-dihydroxybenzoic acid as matrix, diagnostic spectra were obtained on standards, but the presence of soluble low molecular weight polyethylene in extract solutions caused some problems with ionisation suppression. 

Matrix assisted laser desorption ionisation (MALDI) and ESI-MS spectra of non-ionic surfactant blends of AE obtained after positive ionisation were compared [28]. Both the ionisation procedures, which produce [M + Na]+ ion clusters, were very useful for this purpose, but the ESI spectra generated were more complex, whereas MALDI ionisation led to simpler spectra that can be interpreted more easily [28]. 

Figure 16.6—Linear time of flight (TOF) and principle of the reflectron. 1) Sample and sample holder 2) MALDI ionisation device 3 and 3 ) extraction and acceleration grid (5 000 V potential drop) 4) control grid 5) multichannel collector plate 6) electron multiplier 7) signal output. The bottom figure shows a reflectron, which is essentially an electrostatic mirror that is used to time-focus ions of the same mass, but which have different initial energies. This device increases resolution, which can attain several thousand.

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. 

MALDI-TOF MS Matrix-Assisted Laser Desorption Ionisation... 

The mass spectrometer is a mass-flow sensitive device, which means that the signal is proportional to the mass flow dm/dl of the analyte, i.e. the concentration times the flow-rate. It is only now possible to realise the high (theoretically unlimited) mass range and the high-sensitivity multichannel recording capabilities that were anticipated many years ago. Of considerable interest to the problem of polymer/additive deformulation are some of the latest developments in mass spectrometry, namely atmospheric pressure ionisation (API), and the revival of time-of-flight spectrometers (allowing GC-ToFMS, MALDI-ToFMS, etc.). 

Fast atom bombardment (FAB) Plasma desorption (PD) Liquid secondary-ion mass spectrometry (LSIMS) Thermospray (TSP)/plasmaspray (PSP) Electrohydrodynamic ionisation (EHI) Multiphoton ionisation (MPI) Atmospheric pressure chemical ionisation (APCI) Electrospray ionisation (ESI) Ion spray (ISP) Matrix-assisted laser desorption/ionisation (MALDI) Atmospheric pressure photoionisation (APPI) Triple quadrupole (QQQ) Four sector (EBEB) Hybrid (EBQQ) Hybrid (EB-ToF, Q-ToF) Tandem ToF-ToF Photomultiplier... 

Matrix-assisted laser desorption ionisation (MALDI) MH+ (M - H) ToF, IT, FTMS Polar and some nonpolar biopolymers, synthetic polymers >250000... 

Table 6.18 lists the main characteristics of FD-MS. FD is a superior ionisation technique for quantitative analysis, as there are no matrix effects as in LSIMS or MALDI which might suppress the generation of ions from certain additives. However, the technique has some serious drawbacks. The primary difficulty is that FD produces only short-lived, highly variable currents of analyte ions. These analyte ion currents are also very... 

Direct solid-state polymer/additive mass analysis has involved various ionisation modes El (Section 6.2.1), Cl (Section 6.2.2), DCI (Section 6.2.2.1), FAB (Section 6.2.4), FI (Section 6.2.5), FD (Section 6.2.6) and LD. Survey mass spectra obtained with soft ionisation methods (FI-MS, CI-MS) provide diagnostic overviews of chemical composition. The supplemental tandem (MS/MS) and atomic composition (AC-MS) techniques are used to make specific identifications of various organic ingredients. Direct analysis of polymer systems for more than a few thousand daltons has only just begun. Ionisation methods employed are FD, ESI and MALDI. Solid-probe ToF-MS (or DI-HRMS) is a breakthrough [188]. 

This chapter deals mainly with (multi)hyphenated techniques comprising wet sample preparation steps (e.g. SFE, SPE) and/or separation techniques (GC, SFC, HPLC, SEC, TLC, CE). Other hyphenated techniques involve thermal-spectroscopic and gas or heat extraction methods (TG, TD, HS, Py, LD, etc.). Also, spectroscopic couplings (e.g. LIBS-LIF) are of interest. Hyphenation of UV spectroscopy and mass spectrometry forms the family of laser mass-spectrometric (LAMS) methods, such as REMPI-ToFMS and MALDI-ToFMS. In REMPI-ToFMS the connecting element between UV spectroscopy and mass spectrometry is laser-induced REMPI ionisation. An intermediate state of the molecule of interest is selectively excited by absorption of a laser photon (the wavelength of a tuneable laser is set in resonance with the transition). The excited molecules are subsequently ionised by absorption of an additional laser photon. Therefore the ionisation selectivity is introduced by the resonance absorption of the first photon, i.e. by UV spectroscopy. However, conventional UV spectra of polyatomic molecules exhibit relatively broad and continuous spectral features, allowing only a medium selectivity. Supersonic jet cooling of the sample molecules (to 5-50 K) reduces the line width of their... 

PD, LDI, MALDI, etc.) and laser desorption. Recent developments in LC-MS, mainly atmospheric ionisation and off-axis spraying, have made the technique as reliable, versatile and easy to use as capillary GC-MS. 

Many excellent reviews on the development, instrumentation and applications of LC-MS can be found in the literature [560-563]. Niessen [440] has recently reviewed interface technology and application of mass analysers in LC-MS. Column selection and operating conditions for LC-MS have been reviewed [564]. A guide to LC-MS has recently appeared [565]. Voress [535] has described electrospray instrumentation, Niessen [562] reviewed API, and others [566,567] have reviewed LC-PB-MS. For thermospray ionisation in MS, see refs [568,569]. Nielen and Buytenhuys [570] have discussed the potentials of LC-ESI-ToFMS and LC-MALDI-ToFMS. Miniaturisation (reduction of column i.d.) in LC-MS was recently critically evaluated [571]. LC-MS/MS was also reviewed [572]. Various books on LC-MS have appeared [164,433,434,573-575], some dealing specifically with selected ionisation modes, such as CF-FAB-MS [576] or API-MS [577],... 

Principles and Characteristics Problems connected with sample preparation, ionisation and detector efficiency can lead to errors in the quantitation of mass averages and MWD in the case of ESI-MS and MALDI-MS. Coupling of SEC with MS makes it possible to overcome these difficulties. SEC-MS has developed since the early 1990s. Two methods are currently outstanding on-line SEC-ESI-MS (QMS or FTMS) and semi on-line SEC-MALDI-ToFMS [709],... 

As evident from Scheme 7.13, most modern ionisation techniques have been used for TLC-MS, and no single ionisation method is used exclusively with TLC-MS. Various ionisation methods may be applied that avoid the need to evaporate the sample into an El or Cl source these are based in particular on sputtering (FAB, SIMS) or laser desorption. Several sputtering methods of ionisation do not require the use of a liquid matrix, e.g. TLC-SIMS [797], Recent developments include the use of matrix-assisted laser desorption ionisation (MALDI) and surface-assisted laser desorption ionisation (SALDI). It is obvious that TLC-MS is complemented with TLC-MS11 [800] and TLC-HRMS techniques. Table 7.82 lists the general characteristics of TLC-MS. 

Meyer-Dulheuer [55] has analysed the pure additives (phenolic antioxidants, benzotriazole UV stabilisers and HALS compounds) of Table 9.8 in THF solutions by means of MALDI-ToFMS. As it turns out, polar molecules in the mass range of below 800 Da, which have a high absorption coefficient at the laser wavelength used, can often be measured without any matrix [55,56]. In this case, there is no matrix-assisted laser desorption and ionisation (MALDI) process any more. It is a simple laser desorption/ionisation (LDI) process. The advantage of this method is a matrix-free mass spectrum with the same mass resolution as in the MALDI case,... 

Even HALS compounds which absorb weakly at 337 nm can be analysed directly without matrix assistance, with the exception of the high-MW Hostavin N 30 (ca. 1500 Da), which fragments by direct laser desorption ionisation of intact molecules occurs only in the presence of a (dithranol) matrix. Direct laser desorption leads only to noncharacteristic, low-MW fragments. Hostavin N 20 leads to [M + H]+, [M + Na]+, [M + K]+ and some fragmentation peaks. MALDI-ToFMS of Tinuvin 765, which consists of a mono- and bifunctional sterically hindered amine, only shows the adduct peaks of the bifunctional amine apparently, the monofunctional amine is not ionisable. 

Atmospheric pressure ionisation Atmospheric pressure MALDI Atmospheric pressure photo-ionisation Atmospheric pressure spray ionisation... 

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