Mass spectrometry ionisation methods

From the characteristics of the methods, it would appear that FD-MS can profitably be applied to poly-mer/additive dissolutions (without precipitation of the polymer or separation of the additive components). The FD approach was considered to be too difficult and fraught with inherent complications to be of routine use in the characterisation of anionic surfactants. The technique does, however, have a niche application in the area of nonpolar compound classes such as hydrocarbons and lubricants, compounds which are difficult to study using other mass-spectrometry ionisation techniques. 

Dahlmann, J., Budakowski, W.R. and Luckas, B., Liquid chromatography-electrospray ionisation-mass spectrometry based method for the simultaneous determination of algal and cyanobacterial toxins in phytoplankton from marine waters and lakes followed by tentative structural elucidation of microcystins, /. Chromatogr., 994, 1-2, 45, 2003. 

Kallio, H. and Currie, G. (1993a) Analysis of low erucic acid turnip rapeseed oil (Brassica campesteris) by negative ion chemical ionisation tandem mass spectrometry. A method giving information on the fatty acid composition in positions sn-2 and sn- /3 of triacylglycerols. Lipids, 28, 207-15. 

In addition to the wet and optical spectrometric methods, which are often used to analyse elements present in very small proportions, there are also other techniques which can only be mentioned here. One is the method of mass spectrometry, in which the proportions of separate isotopes can be measured this can be linked to an instrument called a field-ion microscope, in which as we have seen individual atoms can be observed on a very sharp hemispherical needle tip through the mechanical action of a very intense electric field. Atoms which have been ionised and detached can then be analysed for isotopic mass. This has become a powerful device for both curiosity-driven and applied research. 

Kasprzyk-Hordern B, Dlnsdale RM, Guwy AJ (2007) Multi-residue method for the determination of basic/neutral pharmaceuticals and illicit dmgs in surface water by solid-phase extraction and ultra performance liquid chromatography-positive electrospray ionisation tandem mass spectrometry. J Chromatogr A 1161 132-145... 

In this chapter, we have chosen from the scientific literature accounts of symposia published at intervals during the period 1920 1990. They are personal choices illustrating what we believe reflect significant developments in experimental techniques and concepts during this time. Initially there was a dependence on gas-phase pressure measurements and the construction of adsorption isotherms, followed by the development of mass spectrometry for gas analysis, surface spectroscopies with infrared spectroscopy dominant, but soon to be followed by Auger and photoelectron spectroscopy, field emission, field ionisation and diffraction methods. 

Mass spectrometry has a number of features and advantages that can make it a very valuable tool for the identification of organic additives in polymers (Table 6.2). The range of products that can be studied is limited by the ionisation method used and the performance of the mass spectrometer. Mass spectrometry... 

Applications Mass spectrometry has often been used more as an auxiliary, rather than a primary, identification method for additives in polymers. Table 6.5 shows the suitability of various ionisation modes for oligomer (and polymer) analysis. 

Principles and Characteristics Ionisation processes are the basis for mass-spectrometric detection. Each of the ionisation techniques occupies its own position in mass spectrometry. The optimum performance of any ionisation method (and therefore the result) will depend critically on the characteristics and reliability of the mass spectrometer. Ionisation may occur in the gas, liquid or condensed phase, and may be either hard or soft , i.e. with or without extensive... 

Electron impact ionisation (El) stands for extensive fragmentation, but also produces molecular ions. The other ionisation methods shown in Table 6.10 mainly generate quasi-molecular ions for various compound classes. Protonation of organic compounds is one of the most fundamental processes of Cl, FAB and ESI mass spectrometry. Apart from electrospray (ESI), which... 

For non-volatile sample molecules, other ionisation methods must be used, namely desorption/ionisation (DI) and nebulisation ionisation methods. In DI, the unifying aspect is the rapid addition of energy into a condensed-phase sample, with subsequent generation and release of ions into the mass analyser. In El and Cl, the processes of volatilisation and ionisation are distinct and separable in DI, they are intimately associated. In nebulisation ionisation, such as ESP or TSP, an aerosol spray is used at some stage to separate sample molecules and/or ions from the solvent liquid that carries them into the source of the mass spectrometer. Less volatile but thermally stable compounds can be thermally vaporised in the direct inlet probe (DIP) situated close to the ionising molecular beam. This DIP is standard equipment on most instruments an El spectrum results. Techniques that extend the utility of mass spectrometry to the least volatile and more labile organic molecules include FD, EHD, surface ionisation (SIMS, FAB) and matrix-assisted laser desorption (MALD) as the last... 

Figure 6.5 Comparison of the selectivity of ionisation methods in mass spectrometry...

Principles and Characteristics Electron impact (El) ionisation is the original ionisation method (1918). Before 1980, mass spectrometry was merely restricted to electron impact (El), with chemical ionisation (Cl) being applied mainly for those samples which resist generation of satisfactory El data. Nowadays, El is still a widely used universal and nonselective ionisation method. In El, the sample is introduced as a vapour... 

In a study on the identification of organic additives in rubber vulcanisates using mass spectrometry, Lattimer et al. [22] used direct thermal desorption with three different ionisation methods El, Cl and FI. Also, rubber extracts were examinated directly by four ionisation methods (El, Cl, FD and FAB). The authors did not report a clear advantage for direct analysis as compared to analysis after extraction. Direct analysis was a little faster, but the extraction methods were considered to be more versatile. 

Applications Early MS work on the analysis of polymer additives has focused on the use of El, Cl, and GC-MS. The major drawback to these methods is that they are limited to thermally stable and relatively volatile compounds and therefore are not suitable for many high-MW polymer additives. This problem has largely been overcome by the development of soft ionisation techniques, such as FAB, FD, LD, etc. and secondary-ion mass spectrometry. These techniques all have shown their potential in the analysis of additives from solvent extract and/or from bulk polymeric material. Although FAB has a reputation of being the most often used soft ionisation method, Johlman el al. [83] have shown that LD is superior to FAB in the analysis of polymer additives, mainly because polymer additives fragment extensively under FAB conditions. 

Recently, Lattimer et al. [22,95] advocated the use of mass spectrometry for direct analysis of nonvolatile compounding agents in polymer matrices as an alternative to extraction procedures. FAB-MS was thus applied as a means for surface desorption/ionisation of vulcanisates. FAB is often not as effective as other ionisation methods (El, Cl, FI, FD), and FAB-MS is not considered particularly useful for extracted rubber additives analysis compared to other methods that are available [36], The effectiveness of the FAB technique has been demonstrated for the analysis of a live-component additive mixture [96]. 

Figure 6.10 Production of positive ions by thermospray ionisation. After Ashcroft [35]. From A.E. Ashcroft, Ionization Methods in Organic Mass Spectrometry, The Royal Society of Chemistry, Cambridge (1997). Reproduced by permission of The Royal Society of Chemistry...

Sample preparation for the common desorption/ionisation (DI) methods varies greatly. Films of solid inorganic or organic samples may be analysed with DI mass spectrometry, but sample preparation as a solution for LSIMS and FAB is far more common. The sample molecules are dissolved in a low-vapour-pressure liquid solvent - usually glycerol or nitrobenzyl alcohol. Other solvents have also been used for more specialised applications. Key requirements for the solvent matrix are sample solubility, low solvent volatility and muted acid - base or redox reactivity. In FAB and LSIMS, the special art of sample preparation in the selection of a solvent matrix, and then manipulation of the mass spectral data afterwards to minimise its contribution, still predominates. Incident particles in FAB and LSIMS are generated in filament ionisation sources or plasma discharge sources. 

ToF analysers are able to provide simultaneous detection of all masses of the same polarity. In principle, the mass range is not limited. Time-of-flight mass analysis is more than an alternative method of mass dispersion it has several special qualities which makes it particularly well suited for applications in a number of important areas of mass spectrometry. These qualities are fast response time, compatibility with pulsed ionisation events (producing a complete spectrum for each event) ability to produce a snapshot of the contents of the source volume on the millisecond time-scale ability to produce thousands of spectra per second and the high fraction of the mass analysis cycle during which sample ions can be generated or collected. 

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... 

Plasmas compare favourably with both the chemical combustion flame and the electrothermal atomiser with respect to the efficiency of the excitation of elements. The higher temperatures obtained in the plasma result in increased sensitivity, and a large number of elements can be efficiently determined. Common plasma sources are essentially He MIP, Ar MIP and Ar ICP. Helium has a much higher ionisation potential than argon (24.5 eV vs. 15.8 eV), and thus is a more efficient ionisation source for many nonmetals, thereby resulting in improved sensitivity. Both ICPs and He MIPs are utilised as emission detectors for GC. Plasma-source mass spectrometry offers selective detection with excellent sensitivity. When coupled to chromatographic techniques such as GC, SFC or HPLC, it provides a method for elemental speciation. Plasma-source detection in GC is dominated by GC-MIP-AES... 

Isotope dilution mass spectrometry (IDMS) can be applied with most of the ionisation methods used in mass spectrometry to determine isotope ratios with greater or lesser accuracy. For calibration by means of isotope dilution, an exactly known amount of a spike solution, enriched in an isotope of the element(s) to be determined, is added to an exactly known amount of sample. After isotopic equilibration, the isotope ratio for the mixture is determined mass spectrometrically. The attraction of IDMS is its potential simplicity it relies only on the measurement of ratios. The... 

Desorption chemical ionisation (DCI) mass spectrometry has been used for detecting additives extracted from polymers [51,52] by a solvent as volatile as possible. To use the DCI probe, 1 -2 iL of the sample, in solution, are applied to the probe tip, composed of a small platinum coil, and after the solvent has been allowed to evaporate at room temperature, the probe is inserted into the source. The sample is then subject to fast temperature ramping. DCI does not seem to be the most suitable mass-spectrometric method for analysis of dissolved polymer/additive matrices, because ... 

There are as yet no signs that the development of mass spectrometry is slowing down. This has consequences for the analyst. Whereas in the past the practitioner of polymer/additive analysis primarily benefited from a good knowledge of chromatography, it is now essential that such analytical scientists are conversant with current MS theory and practice. Advances in MS are due to new conceptual design, new ionisation methods (e.g. switched plasma sources) and... 

---