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A novel experimental technique for tandem mass spectrometry and ion spectroscopy of electrosprayed ions using vacuum-ultraviolet (VUV) synchrotron radiation is presented. Photon activation of trapped precursor ions has been performed by coupling a commercial linear quadrupole ion trap (Thermo scientific LTQ XL), equipped with the electrosprayed ions source, to the DESIRS beamline at the SOLEIL synchrotron radiation facility. The obtained results include, for the first time on biopolymers, photodetachment spectroscopy using monochromated synchrotron radiation of multi-charged anions and the single photon ionization of large charge-selected polycations. The high efficiency and signal-to-noise ratio achieved by the present set-up open up possibilities of using synchrotron light as a new controllable activation method in tandem mass spectrometry of biopolymers and VUV-photon spectroscopy of large biological ions.

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