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MALDI mass spectra of SEC fractions can, for example, be used to calibrate the retention time axis of this separation method, which is a problem in itself. 10 illustrates the procedure. It shows the SEC trace of a polydimethylsiloxane sample, together with MALDI mass spectra of four fractions. Based on the MALDI data, the SEC curve could be calibrated in terms of absolute molar masses, and the molecular mass average of the sample could be computed from the SEC curve [9, 45]. 6 CONCLUSIONS Great progress has been made in a detailed understanding of the MALDI ion formation processes.

Must co-crystallize properly. These conditions are sometimes not met at all, for example, due to solubility issues of high-molecular-weight polymers, which limits the choice of matrix and explains the somewhat exotic substances used for MALDI of polymer samples. The solid–solid sample preparation method presents a viable alternative, and it is expected that common MALDI matrices should be applicable in this case. Other factors, aside from solubility and crystallization, also play some roles in the selection of a proper matrix.

The most important secondary process in polymer MALDI is cationization in the gas phase. For positive ion mode, photoelectrons released from the metal sample support may be deleterious, especially if delayed extraction in a TOF instrument is used. Either a thick sample, covering the metal, or a nonmetallic support should be used. Negative ion MALDI-MS has very little practical significance in the field of polymer MS. Quantitation in MALDI is known to be difficult, but a quantitative response over a wide mass range is precisely what is desired for polymer analysis.

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