PMID- 24745975
OWN - NLM
STAT- MEDLINE
DCOM- 20150814
LR  - 20140520
IS  - 1520-6882 (Electronic)
IS  - 0003-2700 (Linking)
VI  - 86
IP  - 10
DP  - 2014 May 20
TI  - Integrated quantification and identification of aldehydes and ketones in 
      biological samples.
PG  - 5089-100
LID - 10.1021/ac500810r [doi]
AB  - The identification of unknown compounds remains to be a bottleneck of mass 
      spectrometry (MS)-based metabolomics screening experiments. Here, we present a 
      novel approach which facilitates the identification and quantification of 
      analytes containing aldehyde and ketone groups in biological samples by adding 
      chemical information to MS data. Our strategy is based on rapid 
      autosampler-in-needle-derivatization with p-toluenesulfonylhydrazine (TSH). The 
      resulting TSH-hydrazones are separated by ultrahigh-performance liquid 
      chromatography (UHPLC) and detected by electrospray 
      ionization-quadrupole-time-of-flight (ESI-QqTOF) mass spectrometry using a SWATH 
      (Sequential Window Acquisition of all Theoretical Fragment-Ion Spectra) 
      data-independent high-resolution mass spectrometry (HR-MS) approach. 
      Derivatization makes small, poorly ionizable or retained analytes amenable to 
      reversed phase chromatography and electrospray ionization in both polarities. 
      Negatively charged TSH-hydrazone ions furthermore show a simple and predictable 
      fragmentation pattern upon collision induced dissociation, which enables the 
      chemo-selective screening for unknown aldehydes and ketones via a signature 
      fragment ion (m/z 155.0172). By means of SWATH, targeted and nontargeted 
      application scenarios of the suggested derivatization route are enabled in the 
      frame of a single UHPLC-ESI-QqTOF-HR-MS workflow. The method's ability to 
      simultaneously quantify and identify molecules containing aldehyde and ketone 
      groups is demonstrated using 61 target analytes from various compound classes and 
      a (13)C labeled yeast matrix. The identification of unknowns in biological 
      samples is detailed using the example of indole-3-acetaldehyde.
FAU - Siegel, David
AU  - Siegel D
AD  - Department of Pharmacy, Analytical Biochemistry Group, University of Groningen , 
      Antonius-Deusinglaan 1, Building Code XB20, level 6, Groningen, 9713 AV, The 
      Netherlands.
FAU - Meinema, Anne C
AU  - Meinema AC
FAU - Permentier, Hjalmar
AU  - Permentier H
FAU - Hopfgartner, Gerard
AU  - Hopfgartner G
FAU - Bischoff, Rainer
AU  - Bischoff R
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20140505
PL  - United States
TA  - Anal Chem
JT  - Analytical chemistry
JID - 0370536
RN  - 0 (Aldehydes)
RN  - 0 (Ketones)
SB  - IM
MH  - Aldehydes/*analysis
MH  - Calibration
MH  - Chromatography, High Pressure Liquid
MH  - Ketones/*analysis
MH  - Mass Spectrometry
MH  - Metabolomics/methods
MH  - Saccharomyces cerevisiae/chemistry
MH  - Spectrometry, Mass, Electrospray Ionization
MH  - Tandem Mass Spectrometry/methods
EDAT- 2014/04/22 06:00
MHDA- 2015/08/15 06:00
CRDT- 2014/04/22 06:00
PHST- 2014/04/22 06:00 [entrez]
PHST- 2014/04/22 06:00 [pubmed]
PHST- 2015/08/15 06:00 [medline]
AID - 10.1021/ac500810r [doi]
PST - ppublish
SO  - Anal Chem. 2014 May 20;86(10):5089-100. doi: 10.1021/ac500810r. Epub 2014 May 5.