4th EucheMs chemistry congress

Poster Session 2
s1151
chem. Listy 106, s257–s1425 (2012)
Poster session 2 - Analytical Chemistry
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CoMPAriSon of direCt infuSion MASS
SPeCtroMetry, hPLC/MS And ion MoBiLity/MS
in AnALySiS of PoLyACryLiC ACidS
K. SLovAKovA 1 , d. roBertS 2 , t. f. JorGe 3 , M.
h. fLorenCio 3 , K. LeMr 1
1 Palacky University Faculty of Science, Analytical chemistry,
Olomouc, Czech Republic
2 Waters, Atlas Park Simonsway, Manchester, United Kingdom
3 Faculty of Sciences of the University of Lisbon, Chemistry and
Biochemistry Centre, Lisbon, Portugal
Polyacrylic acids (PAA) belong to potential environmental
pollutants due to their extensive use and solubility in water
contributing to their distribution in environment.
The direct infusion and chromatographic experiments were
performed using an LCQ DUO ion trap mass spectrometer
equipped with electrospray ion source (Thermo Finnigan, San
Jose, USA) and an HPLC Agilent 1100 Series chromatograph
(Agilent, USA) with Gemini column (5μm C18, 110 A;
Phenomenex, Torrance, USA). Ion mobility mass spectrometric
experiments were carried out using a SYNAPT G2-S spectrometer
(Waters, Manchester, UK) by flow injection analysis with
negative electrospray ionization.
Direct infusion mass spectrometry using electrospray
ionization in negative ion mode allowed fast detection of several
oligomeric series, but the detail polymer characterization required
time consuming inspection and interpretation of spectra.
Chromatographic separation (LC/MS) is more timeconsuming
but allowed obvious differentiation of oligomeric
series with different end groups. Subsequent LC/MS/MS analysis
contributed to the identification of the end group.
Ion mobility mass spectrometric experiments were used to
provide further structural information by separation of the
individual charge series. It allowed fast characterization of PAA
samples and drift time vs m/z plots can be used as fingerprints for
the differentiation of samples. It is evident that some separation
(ion mobility or chromatographic) is very useful for complicated
PAA mixture analysis. Hyphenation of chromatography, ion
mobility and mass spectrometry can offer a very useful tool for
PAA analysis. Evaluation of orthogonality of chromatographic
and ion mobility is under study.
Acknowledgement: The authors gratefully acknowledge
the support by Palacky University (PrF 2012 020) and by the
Ministry of Education, Youth and Sports of the Czech Republic
(ME10013) and Operational Program Research and Development
for Innovations - European Regional Development Fund
(project CZ.1.05/2.1.00/03.0058), and Fundacio para a Ciencia
e a Tecnologia for financial support (PEst-
OE/QUI/UI0612/2011).
Keywords: Mass spectrometry; Liquid chromatography;
Polymers;
4 th EucheMs chemistry congress
P - 0 5 7 9
SuBStitution of wAter By MethAnoL in
AqueouS norMAL PhASe Liquid
ChroMAtoGrAPhy
J. SouKuP 1 , P. JAnderA 1
1 University of Pardubice, Analytical Chemistry, Pardubice,
Czech Republic
The effects of mobile phase composition on the separation
of phenolic acids on four types of hydrosilated silica columns
(hydrosilated silica, diamond hydride, cholesterol and bidentate
column) in acetonitrile/water and acetonitrile/methanol mobile
phases, both in the ANP and RP modes in the full mobile phase
composition range including both aqueous normal phase (ANP)
and reversed-phase (RP) HPLC modes were investigated. In case
of ANP, the analyte is distributed between a water rich stationary
layer and the bulk mobile phase with a lower water
concentartions, probably by a combination of partition and
adsorption mechanisms. Phenolic acids elute in the order of
increasing polarities i.e. with increasing number of polar groups
(OH, -COOH, etc.) opposite to the reversed-phase mechanism.
The typical mobile phase for ANP chromatography includes
acetonitrile containing 1-15% of buffered or acidified water. We
have found that methanol in buffered mobile phase can substitute
water in the ANP mode. In both types of mobile phases, the
elution order of selected phenolic acids in the ANP mode is
identical and their retention decreases as the concentration of
water or methanol in mobile phase increases. Phenolic acids are
more strongly retained in ACN/methanol on hydrosilated silica
column in comparison to their retention on the same column in
ACN/water mobile phase, whereas the retention of phenolic acids
on cholesterol and diamond column is slightly higher in
ACN/water than in ACN/MeOH. The retention of phenolic acids
on bidentate column is comparable in both mobile phases. Slightly
impaired resolution and selectivity was observed in ACN/MeOH
as the mobile phase in comparison to the ACN/water on all
columns tested.
Acknowledgement: This work was supported by the by the
Grant Agency of the Czech Republic, project P206/12/0398.
Keywords: aqueous normal phase LC; phenolic acids; silica
hydride material;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc