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The photoionization mass spectra in Figure 4a and b show a number of small but broad peaks. These peaks derive from minor fragmentation of ions in the flight tube after ionization of the rotaxane, and can thus not be directly related to the m/z ratio on the x axis.
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Optimization of the desorption conditions primarily involves the reduction of the power of the desorption laser and adjusting the position of the sample bar with respect to the nozzle. Although fine-tuning these parameters leads to a reduction of the width of the resonances, it reduces at the same time considerably the signal-to-noise ratio of the signal, and thus leads to extensive signal averaging
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