:C.

-ammunicatienseit
Mess Spectrometry

Published online in Wiley Online Library

Research Article
Accepted: 4 November 2016
Received: 21 July 2016 Revised: 3 November 2016

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9 metabolomics
l Performance analysis of
i
b comparison grapeberry
r
a of metabolites
r
y electrospray Mauro Commisso,
.
c
ionization Andrea Anesit,
o
r
and Silvia Dal Santo
n
)
atmospheric and Flavia Guzzo*
pressure Biotechnology Department,
D
O chemical University of Verona,
I
: ionization in Strada le Grazie 15, 37134
Verona, Italy
1
untarge-ted
0
.
and RATIONALE:
Electrospray ionization
1 targeted (ESI) and atmospheric
pressure chemical
0
0 ionization (APCI) are
both used to
Untargeted metabolomics based on liquid chromatography/ generate ions for the
mass spectrometry (LC/MS) aims to screen a large proportion
analysis of metabolites
of the non-volatile metabolites in a given biological system.
The most common atmospheric pressure ionization methods by liquid
in this context are electrospray ionization (ESI) and chromatography/mass
atmospheric pressure chemical ionization (APCI). 111 The spectrometry (LC/MS).
c o mb i n a t i o n of t he s e t w o me t h o d s f o r u n t a r ge t e d We compared
metabolomics allows the analysis of a broad range of
metabolites with diverse chemical and physical properties. the performance of these
ESI is particularly efficient for strongly and moderately polar methods for the analysis
metabolites with a large molecular mass, whereas APCI is of Corvina grapevine
mainly used for non-polar and weakly polar metabolites. 121 berry methanolic extracts,
Both EST and APCI are soft ionization methods, i.e. they which are complex
mixtures of diverse
metabolites.
t Present address: Physics Department, Laborator y of
Rapid C0111111101. Mass Sped-rota. 2017, 31, 292-300
* Correspondence
Bioorgani c Cheto: Guzzo,
F. tr
mis Biotechnology
y, Universit Department,
y of Tre nto, Via
Sommarive 14, 38123 Trento, Italy.
University of Verona, Strada le Grazie 15, 37134 Verona,
Italy.
E-mail: flavia.guzzo@univr.it
METHODS: Corvina berries
representing three ripening
stages (veraison, early-
ripening and full-ripening)
were collected during two
growing seasons, powdered
and extracted with
methanol. Untargeted
metabolomic analysis was
carried out by LC/ESI-MS
and LC / APCI-MS.
Processed data files were
assembled into a data matrix
for multivariate statistical
analysis. The limits of
detection (LODs), limits of
quantification (LOQs), linear
ranges, and matrix effects
were investigated for strongly
polar metabolites such as
sucrose and tartaric acid and
for moderately polar
metabolites such as caftaric
acid,
epicatechin and quercetin 3-
0-glucoside.
RESULTS: Multivariate
statistical analysis of the
608 features revealed that
APCI was particularly
suitable for the ionization of
strongly polar metabolites
such as sugars and organic
acids, whereas ESI was more
suitable for moderately polar
metabolites such as
flavanols, flavones and both
glycosylated and acylated
anthocyanins. APCI
generated more fragment
ions whereas ESI generated
more adducts. ESI achieved
lower LODs and LOQs for
sucrose and tartaric acid but
featured narrower linear
ranges and greater matrix
effects.
CONCLUSIONS: ESI and
APCI are not complementary
ion sources. Indeed, ESI can
be exploited to analyze
moderately polar
metabolites, whereas Joh
APCI can be used to n
investigate weakly Wil
polar/non-polar ey
metabolites and, as (Sr
demonstrated by our
Son
results, also strongly
s,
polar metabolites. ESI
and APCI can be used in Ltd.
parallel, exploiting their
strengths to cover the
plant metabolome more
broadly than either
method alone. Copyright
2016 John Wiley &
Sons, Ltd.
generate intact molecular ions or few fragments during
the first round of ionization. These features make them
ideal in research fields such as drug development, disease
monitoring, and the compositional analysis of foods, beverages
and herbal products.
Win e i s a s o u r c e o f h e a l t h - p r o mo t i n g s e c o n d a r y
metabolites, especially antioxidant polyphenols such as
resveratrol and anthocyanins. 131 The molecular composition
wine is strictly related to the fermentation process and
metabolic profile of the grapevine berries, which
depends on the developmental and/or ripening stage
and the pedoclimatic conditions.
developmental phase characterized by rapid cell division
and growth, during which malate and other organic acids
accumulate rapidly in the vacuoles.
a r ipen ing phas e invo lving sug ar ac cumul at ion,
softening, and changes in color, followed by an increase in
pH and th e ac cumul at ion of polyph enol s a nd fl a vor
compounds. 14 '81
Corvina is an Italian grapevine cultivar which is widely
used for the production of Bardolino and Valpolicella wines.
It is also combined with Corvinone and Rondinella berries to
produce premium wines such as Amarone and Recioto after
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op
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ht
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