Coupling of fully automated chip electrospray to Fourier transform ion cyclotron resonance mass spectrometry for high-performance glycoscreening and sequencing

Institute for Medical Physics and Biophysics, University of Münster, Robert Koch Str. 31, 48149 Münster, Germany.
Rapid Communications in Mass Spectrometry (Impact Factor: 2.25). 02/2004; 18(24):3084-92. DOI: 10.1002/rcm.1733
Source: PubMed


The NanoMate robot has been coupled to a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer at 9.4 T and implemented for the first time for complex carbohydrate analysis. It was optimized in the negative ion mode to achieve automated sample delivery on the chip along with increased sensitivity, ultra-high resolution and accurate mass determination. A novel bracket has been designed to allow a reliable mounting of the NanoMate to the Apollo electrospray ionization (ESI) source of an APEX II instrument. The notably higher efficiency of ionization for compositional mapping of complex mixtures and feasibility for fragmentation analysis of components by sustained off-resonance irradiation collision-induced tandem mass spectrometry (SORI-CID MS2) has been demonstrated on a glycoconjugate mixture containing O-glycosylated sialylated peptides from urine of a patient suffering from a hereditary N-acetylhexosaminidase deficiency (Schindler's disease), previously analyzed by capillary-based nanoESI-FTICRMS, and of a healthy control person. Due to its potential to generate highly charged ionic species, reduce the in-source fragmentation, increase sensitivity, reproducibility and ionization efficiency, along with the ability to generate a sustained and constant electrospray, this method can be considered as a new platform for advanced glycomics.

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    • "[13] [14] [15] In some instances , the analysis of the glycopeptides from patient urine was also conducted in comparison with an age-matched healthy control. Out-of-plane robotized nanochip devices for automatic sample infusion by nanoelectrospray ionization (nanoESI), polymer thin microchips for ESI, on-line coupled with either hybrid quadrupole time-of-flight (QTOF) MS, [13] [16] or Fourier transform ion cyclotron resonance (FTICR) MS [17] [18] were optimized and applied for screening and structural analysis of glycans and glycopeptides associated with Schindler condition . Because of the complexity of the mixture, a capillary electrophoresis (CE) technique was also on-line and off-line coupled with QTOFMS for separation, followed by compositional and structural analysis of single components in various fractions from urine of Schindler disease type I patients. "
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