MALDI-TOF

Another very sensitive MS technique is MALDI-TOF. Its high-resolution mass spectra allowed, for example, the identification of the 8-oxo-G lesion by its 416-Da mass shift in a oligonucleotide heptamer at picomol level (Bartolini and Johnston 2000). 

Matrix-assisted iaser desorption ionization time-of-fiight (MALDI-TOF) 

In matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, a UV laser is used to generate atoms, M, of the sample [M + H] or [M + Na] ions are typically detected. It is a soft method and there is little fragmentation. 

Worked example 4.5 MALDI-TOF mass spectrum of a polydimethylsiloxane 

The figure below shows the MALDI-TOF mass spectrum (positive mode) of a sample of a polydimethylsiloxane elastomer, the repeat unit of which is  

Linear polymer chains may be terminated in Me or OH units cyclic oligomers are also possible. 

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Figure 12.9 MALDI-TOF mass spectrum of chicken egg-white lysozyme. The peak at 14,307.7578 daltons (amu) is due to the monoprotonated protein, M+H+, and that at 28,614.2188 daltons is due to an impurity formed by dimerization of the protein. Other peaks are various protonated species, M+H rH ...

Major groove (DNA), 1104-1105 Malate, from fumarate, 221-222 MALDI-TOF mass spectrometry, 417-418... 

Two relatively new techniques, matrix assisted laser desorption ionization-lime of flight mass spectrometry (MALDI-TOF) and electrospray ionization (FS1), offer new possibilities for analysis of polymers with molecular weights in the tens of thousands. PS molecular weights as high as 1.5 million have been determined by MALDI-TOF. Recent reviews on the application of these techniques to synthetic polymers include those by Ilantoif54 and Nielen.555 The methods have been much used to provide evidence for initiation and termination mechanisms in various forms of living and controlled radical polymerization.550 Some examples of the application of MALDI-TOF and ESI in end group determination are provided in Table 3.12. The table is not intended to be a comprehensive survey. 

Table 3.12 Application of MALDI-TOF or ESI Mass Spectrometry to Polymers Prepared by Radical Polymerization...

Conventional - with catalytic chain transfer MALDI-TOF PMMA, copolymers 0 - 5 ... 

Conventional, AIBN - wnth transfer to solvent MALDI-TOF PNVp. M... 

Hensley ei al.,n reported the only direct experimental observation of head-to-head linkages in PS by 2D INADEQUATE NMR on, 3C-enriched PS. The method did not enable these groups to be quantified with sufficient precision for evaluation of W tc- Zammit el a/.130 studied chain distribution of low molecular weight PS prepared with AIBN initiator by MALDI-TOF. Separate distributions of chains formed by combination and disproportionation were observed. They estimated kJkK. at 90 °C to be 0.057. 

The nature of the termination reaction in MMA polymerization has been investigated by a number of groups using a wide range of techniques (Tabic 5.5), There is general agreement that there is substantial disproportionation. However, there is considerable discrepancy in the precise values of k tk. In some cases the difference has been attributed to variations in the way molecular weight data are interpreted or to the failure to allow for other modes of termination under the polymerization conditions (chain transfer, primary radical termination).154 In other eases the reasons for the discrepancies are less clear. MALDI-TOF mass... 

The molecular weights and molecular weight distributions (MWD) of phenolic oligomers have been evaluated using gel permeation chromatography (GPC),23,24 NMR spectroscopy,25 vapor pressure osmometry (VPO),26 intrinsic viscosity,27 and more recently matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS).28... 

Mandal and Hay28 used MALDI-TOF mass spectrometry to determine the absolute molecular masses and endgroups of 4-phenylphenol novolac resins prepared in xylene or chlorobenzene. Peaks with a mass difference of 44 (the molecular weight of a xylene endgroup) suggested that reactions conducted in xylene included some incorporation of xylene onto the chain ends when a strong acid such as sulfuric acid was used to catalyze the reaction. By contrast, no xylene was reacted into the chain when a milder acid catalyst such as oxalic acid was used. No chlorobenzene was incorporated regardless of the catalyst used. 

During the past decade, MALDI-TOF MS has proven to be an effective tool for the analysis of oligo- and polymeric mannoglucans (for extensive reviews see [222,223]). SEC/MALDI mass spectrometry was employed in the analysis of hemicelluloses isolated by microwave heat-fractionation from spruce and aspen wood [94]. These methods allowed the separation and characterization of the oligo- and polysaccharide fractions derived from the xylan and mannan components of both woods [224]. 

MALDI-TOF matrix-assisted laser desorption ionization time of flight... 

MALDI-ToF is a technique that allows the molecular weights of proteins and peptides to be determined. It is less susceptible to suppression effects than electrospray ionization and thus is able to be used for the direct analysis of mixtures. In the case of a crude tryptic digest, MALDI-ToF will provide a molecular weight profile of the polypeptides present without the analysis time being extended by the need to use some form of chromatographic separation. 

Figure 5.19 MALDI-ToF mass spectrum, providing a molecular-weight profile of the tryptic peptides derived from spot 22 (see Figure 5.18) of the silver-stained two-dimensional gel of the proteins extracted from the yeast S. cerevisiae. From Poutanen, M., Salusjarvi, L., Ruohonen, L., Penttila, M. and KaUddnen, N., Rapid Commun. Mass Spectrom., 15, 1685-1692, copyright 2001. John Wiley Sons Limited. Reproduced with permission.

The fact that only ethylene and tetramethylethylene are evolved from exp-[8]rotane 168 and permethyl-exp-[6]rotane 173 upon thermal decomposition leads to the conclusion that the spirocyclopropane moieties in these expanded [n]rotanes fragment only externally and leave carbene moieties behind. Indeed, the MALDI-TOF mass spectra of several exp-[ ]rotanes show fragment ions with M minus 28. Thus, if this fragmentation in an exp-[n]rotane were to continue n times, a cyclic C carbon cluster would be left over. So far, however, a fragment ion with m/z = 480 corresponding to 182 has not been recorded in the mass spectrum of exp-[8]rotane 168 and it remains to be seen whether a Cgo cluster 183 will be detected in the mass spectrum of exp-[12]rotane 171 (Scheme 35). 

The MALDI-TOF mass spectra of the Cso-fullerene-annelated [3]- and [4]rotanes 127 and 128 also demonstrated that these molecules fragment at the spirocyclopropane units with successive loss of the fullerene moieties. Unfortunately, however, the peaks for cyclo-Ci and cyclo-C2o carbon clusters were not observed [38]. 

Scheme 3. J efro-addition of 23 and 24 under MALDI-TOF MS conditions generates the ions of the mono-fullerene adducts of cydo-Ci (25" ) and cydo-C.20 (26" ), respectively [61]...

Considering these situations, the observation of molecular weights, particularly by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MASS), is essential [33]. The operation is simple and enables us to observe the molecular ion peaks of CPOs with molecular weights exceeding 10,000. The quahty of the measurement is strongly dependent on the choice of the matrix. Therefore, the search for the best matrix for each CPO should be pursued. 

However, because of the high price, MALDI-TOF mass spectrometers have not come into wide use. Vapor pressure osmometry (VPO), an old and traditional method for estimating molecular weight, is useful in the field of CPO chemistry. The experimental error of this measurement is approximately 10% however, the obtained data are sufficiently useful to estimate the number of porphyrins in a molecule. 

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