static.uni-graz.at2016/06/11 · 10 th - 11 June 2016, University of Graz 9 Foreword Dear Collegues and Students, it is our pleasure to welcome you at the 12th ASAC JunganalytikerInnenforum

7 10th

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June 2016, University of Graz

Supporting Agencies

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ASAC JunganalytikerInnenforum 8

12th

ASAC JunganalytikerInnenforum – Book of Abstracts

Edited by

University of Graz

Institute of Chemistry, Department of Analytical Chemistry

Analytical Chemistry for Health and Environment (ACHE)

Universitätsplatz 1

8010 Graz, Austria

Organizing Committee

Dr. Walter Goessler

Simone Braeuer, MSc

Lisa Fasshold, MSc

Mag. Kathrin Ertl

Oliver Steiner, BSc

Stefan Tanda, MSc

Christoph Walcher, MSc

Book of Abstracts: Stefan Tanda, MSc

Printed by: ÖH-Uni Graz GmbH

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Foreword

Dear Collegues and Students,

it is our pleasure to welcome you at the 12th ASAC JunganalytikerInnenforum of the Austrian

Society of Analytical Chemistry here in our completely renovated institute of chemistry in Graz.

We hope that the forum will provide plenty of room for lively discussions on latest results

presented by young scientists in the field of analytical chemistry.

We are looking forward to spending with you two enjoyable days, offering a wealth of

opportunities to get together during coffee breaks and the conference dinner in a typical

Styrian Buschenschank.

The Organizing Committee wishes to thank our sponsors and exhibitors for their support and

wishes you a successful scientific meeting.

On behalf of the Organizing Committee yours,

Walter Goessler

University of Graz, Institute of Chemistry, Department of Analytical Chemistry

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Table of Contents

Foreword ........................................................................................................... 9

Table of Contents ............................................................................................ 10

Venue Map ...................................................................................................... 11

Programme ..................................................................................................... 12

Abstracts ......................................................................................................... 17

Conference Opening and Impulse Lecture ................................................. 18

Session I - Environment ............................................................................... 20

Session II - Sensors ...................................................................................... 25

Session III - Health ....................................................................................... 30

Session IV - Environment ............................................................................ 35

Session V - Metabolomics ........................................................................... 40

Session VI - Food ......................................................................................... 46

List of Participants ........................................................................................... 51

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Venue Map

University of Graz

Universitätsplatz 1, ground floor

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Programme

Friday 10th

June 2016

Location: University of Graz, Universitätsplatz 1, Ground Floor, HS 03.01

12:00 - 13:30 Registration

13:30 - 13:40 Welcoming Words

13:40 - 14:25 Impulse Lecture

Heiko Egenolf

BASF SE, Competence Center Analytics, Ludwigshafen, Germany

Thi k ig! – Analytics on the i dust ial s ale

14:25 - 14:40 Short Break

Session I: Environment - Chair: Kathrin Ertl

14:40 - 15:00 Anna Rathgeb BOKU Vienna

From the peat bog to the open ocean: investigation of Natural organic Matter as metal carrier by non-targeted LC-ESI-TOFMS

15:00 - 15:20 Samuele Zoratto

Vienna University of Technology

Imaging of fungal metabolites by MALDI Ion Mobility MS

15:20 - 15:40 Leila Maringer Johannes Kepler University, Linz

Study of polymer stabilizers and their interaction mechanisms using HPLC-MS

15:40 - 16:00 Maria Moßhammer

Technical University of Graz

Multi-analyte imaging on complex biological samples such as microbial mats and below ground tissue of seagrasses

16:00 - 16:20 Coffee Break

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Session II: Sensors - Chair: Christoph Walcher

16:20 - 16:40 Eva Fritzsche Technical University of Graz

Autonomous optical measurement of pH, CO2 and oxygen in the marine environment

16:40 - 17:00 Josef Ehgartner Technical University of Graz

Online analysis of oxygen and pH inside microfluidics with optical sensors

17:00 - 17:20 Bernhard Müller

Technical University of Graz

Fluorescence optical sensors for the measurement of K+ ions

17:20 - 17:40 Wim Cuypers University of Vienna

Defining the synergetic pattern of composites for sensing volatile organic compounds

18:00 - 23:00 Social Event - Conference Dinner

Buschenschank Skoff

Kranach 96 (Skoffweg)

A-8462 Gamlitz

Departure by bus: approx. 18:00

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Saturday 11th

June 2016

Location: University of Graz, Universitätsplatz 1, Ground Floor, HS 03.01

Session III: Health I - Chair: Lisa Fasshold

09:00 - 09:20 Lisa Emhofer Johannes Kepler University, Linz

Uptake and metabolism of non-steroidal anti-inflammatory drugs in cress and radish

09:20 - 09:40 Anastasiya Svirkova

Vienna University of Technology

Sample preparation of sections with undecalcified bone for multimodal MALDI-MS and µ-XRF imaging

09:40 - 10:00 Luis Galvez University of Vienna

Platinum speciation analysis addressing metallodrug-protein interaction in preclinical anticancer research

10:00 - 10:20 Maximilian Aigner

University of Graz

Inhibition-based human monoamine oxidase B biosensors for the determination of MAO B inhibitors


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Session IV: Health II - Chair: Stefan Tanda

10:40 - 11:00 Anna Balbekova Vienna University of Technology

Combination of FTIR and LA-ICP-MS micro-imaging techniques for the study of a tumor treated with sunitinib and cisplatin

11:00 - 11:20 Dominik Braun University of Vienna

Towards the development of a LC-MS/MS multi-method for the quantification of mycotoxins in human breast milk

11:20 - 11:40 Nina Kröpfl University of Graz Analytical method development for selenoneine using model compounds

11:40 - 12:00 Michael Stiboller

University of Graz Arsenic species in human milk

12:00 - 12:30 Lunch

Session V: Metabolomics - Chair: Simone Braeuer

12:30 - 12:50 Alexandra Simader

BOKU IFA

Elucidating the fungal attack of Fusarium graminearum against wheat: insights from a metabolomics time series experiment

12:50 - 13:10 Maria Doppler BOKU IFA

Combining tracer based and global stable isotopic labelling for untargeted metabolomics of Fusarium head blight on wheat

13:10 - 13:30 Michaela Schwaiger

University of Vienna

Anion-exchange chromatography coupled to high resolution mass spectrometry in metabolomics

13:30 - 13:50 Michaela Fischer

BOKU IFA Untargeted Metabolomics of Bo eo s E plodi g A ts

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13:50 - 14:10 Benedikt Putz Vienna University of Technology

Challenges in targeted metabolomics – a comparison of capillary GC and LC triple quadrupole MS


Session VI: Food - Chair: Oliver Steiner

14:30 - 14:50 Brigitte Jaksa Technical University of Graz

Identification of odor active NIAS (non-intentionally added substances) in food contact material

14:50 - 15:10 Andrea Jurek Technical University of Graz

Closer looking to mineral oil hydrocarbons (MOSH/MOAH) in paper packaging used for food contact

15:10 - 15:30 Valerian Kalb Technical University of Graz

Horseradish – a challenging method development

15:30 - 15:50 Iris Tauber Technical University of Graz

F esh, jui , “t ia – the flavour of the old apple variety Ilze ‘ose

15:50 - 16:00 Short Break

16:00 - 16:20 Awards, Closing Ceremony

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Abstracts

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Conference Opening and Impulse Lecture

Walter Goessler & Heiko Egenolf

Friday 10th

June 2016, 13:30 - 14:25

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“Thi k ig! – Analytics on the industrial scale“

Heiko Egenolf

BASF SE, Competence Center Analytics, GMC/AE - M320, Ludwigshafen, Germany

At BASF, we create chemistry for a sustainable future. Our portfolio ranges from chemicals, plastics,

pe fo a e p odu ts a d op p ote tio p odu ts to oil a d gas. As the o ld s leadi g he i al

company, we combine economic success with environmental protection and social responsibility. The

112,000 employees in the BASF Group work on enabling the success of our customers in nearly every

i dust . BA“F ge e ated sales of o e tha €7 illio i . Mo e i fo atio at . asf. o .

With the Competence Center Analytics, BASF operates a central unit with 350 employees that are solving

all kind of analytical problems of research, development, and production. Three factors determine the

excellence of an analytical service provider; quality, speed and analysis costs. Short turnover times in

compliance with the required quality standards at reasonable prices are key factors determining long-term

success in the analytical market.

The high amount of analysis samples processed at the Competence Center Analytics – approx. 250,000 per

year – requires efficient organization of the structures and workflows in the laboratories. Using the

example of the atomic spectrometry lab, some insights will be given into the method portfolio covering

outi e tasks as ell as usto ized solutio s fo spe ial a al ti al p o le s. A other key feature for the

lab optimization has been the development and construction of robotic analysis systems for sample

preparation and measurement. The modes of operation, and the benefits of the robotic systems are

shown.

BASF employs a workforce of over 39,000 at its headquarters in Ludwigshafen (on the Rhine) in

southwestern Germany. This research and production site offers many entry levels, development and

career options, which will be basically explained in the second part of the lecture.

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Session I - Environment

Chair: Kathrin Ertl

Friday 10th

June 2016, 14:40 - 16:00

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From the peat bog to the open ocean: investigation of Natural Organic Matter as

metal carrier by non-targeted LC-ESI-TOFMS

Anna Rathgeba, Tim Causona, Regina Krachlerb, Stephan Hanna

a Department of Chemistry, University of Natural Resources and Life Sciences - BOKU Vienna, Austria

b Institute of Inorganic Chemistry, University of Vienna, Austria

Land-derived Dissolved Organic Matter is able to transport iron and other trace metals from Natural

Organic Matter-rich areas like peat bogs via rivers to the open ocean and can therefore contribute to the

iron supply of marine organisms. This was a remarkable finding several years ago because iron deficiency

represents a growth limiting factor in many regions of the world ocean due to the low solubility of iron (III)

in seawater. Dissolved iron is almost entirely bound to organic ligands of poorly understood structure and

the land-derived substances among them are in the focus of our interest.

In the present study, estuarine mixing zone samples from the Halladale River, peat-influenced samples

from the Craggie burn, which is a tributary of the Halladale River (UK), and a freeze dried Natural Organic

Matter sample from the Suwannee River (Georgia) obtained from the International Humic Substance

Society were investigated by accurate mass RP/HILIC-ESI-TOFMS. Non-targeted data evaluation employing

state-of-the-art feature detection and alignment tools was performed. It could be shown that the three

investigated samples share a significant proportion of the annotated features though they vary in

seawater content and origin. Moreover several components of the Suwannee River sample could be

identified via authentic standards.

Acknowledgement: This project is financed by FWF (P25849 Nanoscale lignin particles as iron chelators in

the ocean).

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Imaging of Fungal Metabolites by MALDI Ion Mobility MS

Samuele Zoratto, Günter Allmaier, Martina Marchetti-Deschmann

Institute of Chemical Technologies and Analytics, Vienna University of Technology), Austria

As an alternative to chemical pesticides against plant pathogenic fungi, some Trichoderma species such as

T. atroviride are capable of inducing plant resistance and are involved in direct mycoparasitism of

pathogens. One group of highly active compounds in these processes are peptaibols. These bioactive

peptides are characterized by unusual amino acids (e.g. α-aminoisobutyric acid), N-terminal (e.g.

acetylation) and C-terminal modifications (e.g. hydroxylation). In this study, the lateral distribution of

peptaibols during fungal interaction has been investigated. We aimed to obtain information on time-

dependent metabolite secretion. This information will help to assess bioavailability of certain peptaibols,

which will later allow interpreting their role during fungal communication/interaction.

T. atroviride was chosen as biocontrol strain and Rhizoctonia solani as a plant pathogen. The fungi were

grown in a miniaturized confrontation assay on a solid potato dextrose agar medium on glass slides.

MALDI mass spectrometry imaging (MSI) in combination with ion mobility separation (IMS) experiments

were carried out after sample drying and matrix coating (2,5-dihydroxybenzoic acid) by sublimation. For

this study a Waters Synapt G2 equipped with a MALDI source was employed. MSI is a powerful tool that

allows the parallel analysis of multiple biomolecules while retaining their spatial localization. The

implementation of IMS allows separating analytes of interest from unwanted background signals

desorbed/ionized from the sample surface by separating the ions in the gas-phase according to their size,

molecular mass and charge number. In combination with a RTOF analyzer, MALDI-IMS-MSI allowed for the

detection, localization and identification of peptaibols, latter by low energy CID, directly from the sample

surface.

Acknowledgment: We acknowledge Susanne Zeilinger (Univ. Innsbruck) for her valuable support, UniInfra

IV (BMWFW) and two Innovative Projects (TU Wien) for instrumentation.

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Study of polymer stabilizers and their interaction mechanisms using HPLC-MS

Leila Maringera, Lukas Roiserb, David Nitschec, Gernot Wallnerd, Wolfgang Buchbergera

a Institute of Analytical Chemistry, JKU Linz, Austria

b Institute of Organic Chemistry, JKU Linz, Austria

c Institute of Polymeric Materials and Testing, JKU Linz, Austria

d AGRU Kunststofftechnik GmbH, Bad Hall, Austria

Hindered amine light stabilizers (HALS) are a widely used class of stabilizers protecting polymeric materials

against UV as well as thermal radiation-induced degradation. Experiments done in the polypropylene-

mimicking model compound squalane showed that HALS may undergo antagonistic as well as synergistic

interactions with phenolic antioxidants depending on the kind of aging. Whereas the thermal radiation-

induced antagonism is well understood [1], not much work has been published about the UV-initiated

synergism between these two stabilizer classes. Within this work, different combinations of HALS with the

phenolic antioxidant Irganox 1330 were analyzed with regard to stabilization efficacies and formed

stabilizer degradation products using high-performance liquid chromatography (HPLC) coupled to UV and

high-resolution mass spectrometric (MS) detection. It was shown that after 176 h, all stabilizer

formulations undergoing a synergism contained oxidized phenolic antioxidants while no intact/oxidized

phenols were detected in the samples exhibiting an antagonism. Comparing the UV absorption spectra of

intact and oxidized Irganox 1330 revealed a shift in the absorption maxima towards higher wavelengths, as

it is typical for commercially available UV absorbers. The observed synergism between HALS and phenolic

antioxidants was therefore assigned to the formation of quinones (oxidized phenols) acting as UV

absorbers, thereby protecting the squalane from undergoing degradation. Indeed, stabilizer efficacy tests,

done with a synthesized model compound, confirmed the UV protecting properties of oxidized phenolic

antioxidants.

References

[1] Vyprachtický D. et al., Polym. Degrad. Stabil., 27, (1990) 227-255.

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Multi-Analyte Imaging on Complex Biological Samples such as Microbial Mats and

Below Ground Tissue of Seagrasses

Maria Moßhammera,b, Jakob Santnerc, Michael Kühlb, Klaus Korenb, Sergey Borisova,

Ingo Klimanta

a Institute for Analytical Chemistry and Food Chemistry, Graz University of Technology, Austria

b Marine Biological Section, Department of Biology, University of Copenhagen, Helsingør, Denmark

c Institute of Soil Research, Department of Forest and Soil Sciences, University of Natural Resources and

Life Sciences, Vienna, Tulln, Austria

In the immediate environment surrounding the roots of seagrass, numerous different processes take place

in order to protect the plant against phytotoxins, such as H2S, but also to ensure nutrient uptake. Oxygen is

transported from the above to the below ground tissue to build oxic microzones in the anoxic sediment

surrounding and thus protecting the roots. Increased pH levels have been observed in the rhizosphere of

some seagrasses and are suspected to play a role in the detoxification of H2S via shifting the chemical

sulfide speciation [1]. In order to measure changes in pH and O2 concentrations simultaneously, a novel

optode system for dual imaging was developed and tested on microbial mats, sampled in Rønbjerg,

Denmark. Eu(HPhN)3dpp was used as O2 sensitive dye, emitting in the red range of the electromagnetic

spectrum, Bu3Coum as reference dye emitting in the green range, and an aza-BODIPY as pH sensitive dye

emitting in the NIR range. The system was optimized in order to minimize cross talk between the channels,

reduce background interferences, and allow a combination with DGT and DET gels for the quantitative

determination of sulfide, phosphate and Fe(II) in the rhizosphere. Sulfide determination was conducted in

a newly designed approach using a hydrogel D4 matrix. The determination of the phosphate concentration

was conducted via a modified method where Zr-oxide is precipitated in a DGT gel. Different sediments and

seagrass roots were investigated in the course of this study.

References

[1] Brodersen K., Nielsen D., Ralph P., Kühl M., New Phytol., 205, (2015) 1264-1276.

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Session II - Sensors

Chair: Christoph Walcher

Friday 10th

June 2016, 16:20 - 17:40

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Autonomous optical measurement of pH, CO2 and oxygen in the marine

environment

Eva Fritzschea, Christoph Staudingera, Martin Strobla, Jan P Fischerb, Jens Müllerc,

Sergey M Borisova, Ingo Klimanta

a Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Graz, Austria

b PyroScience GmbH, Aachen, Germany

c Department of Marine Chemistry, Leibniz Institute for Baltic Sea Research, Rostock, Germany

Since the start of the industrialization in the late 18th century, the atmospheric level of carbon dioxide

increased by about 40%, due to fossil-fuel burning and deforestation. Almost a half of the

anthropogenically produced carbon dioxide is taken by the ocean [1], which leads to a pH reduction of the

seawater. This effect is called ocean acidification. To quantify the changes and the impact on the marine

organisms, an autonomous, sensitive and accurate measurement of the pH and carbon dioxide

concentration is necessary. We developed optodes based on aza-BODIPY dyes for the determination of pH

and the carbon dioxide concentration in seawater. The dyes show absorption and emission in the near

infrared region, which makes them suitable for the use of the Firesting read out devices (PyroScience

GmbH, Aachen). Additionally the sensing materials were optimized in respect to matrix composition and

drift behaviour, as well as mechanical and long-term stability. Temperature and salinity dependencies

were determined. Finally the se so s e e tested du i g the field t ip P‘O“ID i the o the Balti

Sea.

References

[1] Sabine, C. L. et al., Science, 305, (2004) 367-371.

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Online analysis of oxygen and pH inside microfluidics with optical sensors

Josef Ehgartnera, Martin Strobla, Philipp Sulzera, I.Bogachan Tahirbegib, Alice Kasjanowb,

Birgit Ungerböcka,c, Knut Rennertd, Alexander S. Mosigd, Torsten Mayra

a Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Graz, Austria

b iX-factory GmbH, Dortmund, Germany

c microfluidic ChipShop GmbH, Jena, Germany

d Institute of Biochemistry II, University Hospital Jena, Jena, Germany

Optical sensors are highly suitable for microfluidic applications due to their high sensitivity, ability of

contactless readout, ease of miniaturization and their low cost. Therefore, we demonstrate in various

examples of our work the practicability of optical oxygen and pH sensors in microfluidic devices. We

integrated optical oxygen sensors into microreactors and used them for online monitoring of enzyme

reactions, including D-alanine or D-phenylalanine oxidized by D-amino acid oxidase, and glucose oxidation

by glucose oxidase. The developed sensor set-up allows online measurements down to a sensor spot size

of 100 µm in diameter. The oxygen sensitivity of the sensors can be tuned by using different indicator

dyes. The sensors were also integrated into an organ-on-a-chip device for monitoring cell respiration of a

three-dimensional liver organoid and for the determination oxygen in microfluidic droplets for cell culture

experiments. Furthermore, we present nanoparticles for simultaneous monitoring of pH and oxygen.

Figure 1 Measurement set-up consisting of an USB oxygen meter, a microfluidic chip and a chip holder.

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Fluorescence Optical Sensors for the Measurement of K+ Ions

Bernhard Müller, Sergey M. Borisov and Ingo Klimant

Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Graz, Austria

Potassium (K+) is one of the key analytes for clinical diagnostics as it plays a vital role in normal cell

function and various diseases, therefore continuous or sequential monitoring of K+ in whole blood or

serum is of high interest.

Selective detection of low extracellular potassium concentrations (5mM) in blood over high Na+

concentrations (150 mM) is crucial in order to design a sensor for clinical diagnostics. Other challenges

beside good selectivity and high sensitivity for potassium are to eliminate pH cross-sensitivity and have

excitation at longer wavelengths in order to prevent background fluorescence of blood [1].

In this contribution we present new sensing materials for the selective measurement of K+-ions in water.

An aza-crown-ether bound to a phenyl group with an additional ether group in ortho-position for

increasing the K+/Na+ selectivity was used as a receptor [2]. The aromatic amine of the crown shows no pH

cross sensitivity in the physiological range and is responsible for the signal enhancement in presence of K+

due to the reduction of photoinduced electron transfer (PET).

A family of new BODIPY based indicators was designed with tuneable optical properties (excitation

possible from blue to red light) and PET efficiencies. These new indicator dyes are immobilized into

different hydrogel matrices to obtain a stable and robust optical sensor for K+ ions. The preparation of

water dispersible nanoparticles enables imaging or microfluidic applications. Due to a modular system it is

also possible to prepare sensor materials for other ions (e.g. Li+, Na+, Ca2+).

References

[1] He H., Mortellaro M. A., Leiner M. J. P., Fraatz R. J., Tusa J. K., J. Am. Chem. Soc., 125 (6), (2003) 1468-

1469.

[2] Ast S., Schwarze T., Müller H., Sukhanov A., Michaelis S., Wegener J., Wolfbeis O. S., Körzdörfer T.,

Dürkop A., Holdt H.-J., Chem. - Eur. J., 19 (44), (2013) 14911-14917.

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Defining the synergetic pattern of composites for sensing volatile organic

compounds

Wim Cuypers, Purim Jarujamrus, Peter Lieberzeit

University of Vienna, Department of Analytical Chemistry – Chemical Sensors and Rapid

Analysis

Volatile organic compounds (VOCs) are often considered an incalculable cause for disorders such as sick

building syndrome (SBS) [1]. For this reason, there is a high need for sensors detecting these chemicals at

relevant concentrations. Preliminary experiments demonstrated the feasibility of detecting VOCs through

recognition by a combination of polyurethane (PU) molecularly imprinted polymers (MIPs) and silver

sulfide (Ag2S) nanoparticles [2]. Inspired by the synthesis of Ag2S layers formed on polypropylene by

Krylova in 2013 [3], a novel synthesis method for Ag2S NPs is presented here. Furthermore, the response

pattern of both MIPs and composites has been evaluated using a quartz crystal microbalance (QCM) for

various concentrations of 1-butanol. Dropwise addition of silver nitrate (AgNO3, 8mM) to sodium

thiosulfate (Na2S2O3, 20mM) results in the formation of Ag2S NPs. Morphology and composition of these

nanostructures are analyzed by means of scanning electron microscopy (SEM). NPs are then isolated and

incorporated in a PU-MIP network that sensitively binds 1-butanol and QCM is used to evaluate the

binding pattern of the vapor. An identical evaluation is made for MIPs alone. SEM results indicate the

formation of Ag2S NPs. Increasing concentrations of 1-butanol yield larger responses after standardization

to the same layer height. After correction for layer thickness, the response ratio of composite is the double

of the MIP signal over the whole range from 1000 to 3500 ppm. Repeated experiments have shown no

significantly different QCM results, highlighting the reproducibility of this set-up. Ag2S NPs can be

synthesized by an alternative method avoiding drawbacks associated with other techniques (i.e. H2S

method). It bypasses the workplace safety issues related to H2S and moreover, it allows for a more

controlled chemical reaction. MIP composites with such nanoparticles yield higher gravimetric responses

compared to the MIPs alone. In the future, the prospect is to further optimize the detection limit of the

small organic compounds. Besides, selectivity has to be assessed based on experiments towards molecules

with same chain length, but different functionality (i.e. butanethiol), or same functionality, but different

steric properties.

References

[1] Barmark M., Int. J. Environ. Health Res., (2014) 1-18.

[2] Mustafa G., Lieberzeit P., RSC Advances, 4(25), (2014) 12723-8.

[3] Krylova V., Dukštie ̇ N., J. Chem.-NY, (2013) 1-11.

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Session III - Health I

Chair: Lisa Fasshold

Saturday 11th

June 2016, 09:00 - 10:20

31 10th

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Uptake and metabolism of non-steroidal anti-inflammatory drugs

in cress and radish

Lisa Emhofer, Wolfgang Buchberger, Christian W. Klampfl

Institute of Analytical Chemistry, Johannes Kepler University Linz, Linz, Austria

Due to the intense medication in human and in veterinary medicine, pharmaceutically active compounds

(PhACs) can be found in the aquatic system. Sources of contamination are manifold: Parts of the

substances are excreted in their original form or as metabolites after consumption, drug containing gels

for external application are washed off during personal hygiene, or just improper disposal of

pharmaceuticals, resulting in their occurrence in the municipal waste water system. Despite its purification

in wastewater treatment plants, not all contaminants can be removed successfully and thus remain in the

water. If this contaminated water is subsequently used for plant irrigation, crops come into direct contact

and may interact with these substances, causing undesired modification of (edible) plants.

In this work we investigated how plants deal with xenobiotic substances, when irrigated with drug

containing water. Special emphasis was set on the uptake and further metabolism of the PhACs in the

plants. Therefore, cress and radish were cultivated by irrigation with water spiked with four different non-

steroidal anti-inflammatory drugs (diclofenac, naproxen, ketoprofen, mefenamic acid). Extracts of the

treated plants were separated using RP-HPLC followed by high resolution mass spectrometric detection.

Parent drugs as well as several metabolites were detected in both plants. We were able to identify

hydroxylation and glycosylation products as well as conjugates with malonic acid of the latter. As a further

topic the distribution of the parent drug and its metabolites in different parts of the plant was

investigated. Hereby we found that concentrations were highest in the root material of the plants.

12th


Sample preparation of sections with undecalcified bone for multimodal MALDI-MS

and µ-XRF imaging

Anastasiya Svirkovaa, Anna Turyanskayab, Christina Strelib, Martina Marchetti-Deschmanna

a Institute of Chemical Technology and Analytics (CTA), TU Wien, Vienna, Austria

b Atominstitut, TU Wien, Vienna, Austria

Matrix-assisted laser desorption-ionization mass spectrometry imaging (MALDI-MSI) and micro X-ray

fluorescence (µ-XRF) imaging are techniques successfully used to examine the spatial context of molecules

and elements, respectively. We established a sample preparation workflow suitable for consistent MALDI

MSI and µ-XRF imaging of objects containing undecalcified bones and soft tissues.

Chicken toes (purchased from a local market) were used as a representative material of sample containing

hard and soft matter. In order to maintain structural integrity a lot of aspects have been taken into

account. (1) Proper embedding medium for cryosectioning plays an important role, especially when

objects are fragile specimens or contain parts of different hardness. Several media including Tragacanth,

gelatine and sodium carboxymethyl cellulose (NaCMC) and their mixtures of different concentrations were

tested in respect to tissue adhesion, viscosity and therefore pouring performance, easiness of cutting and

durability of cut tissue section. A hydrogel containing NaCMC 5% and Gelatin 20% (w/v) was finally chosen

due to its properties. (2) In a second step proper knives for sectioning have to be selected. Disposable

blades, non-disposable stainless-steel and tungsten carbide knives were used together with a CryoStar

NX50 (Thermo Scientific). Adhesive tape for accurate handling of the tissue was necessary. (3) In the end,

obtained tissue sections have to be tested for their suitability to perform MALDI MSI and µ-XRF imaging

from the very same section.

Information about the distribution of phosphatidylcholines in soft tissue surrounding the bone was

obtained on a Synapt G2 HDMS (Waters, UK) after matrix dithranol was sublimed with a home-built

apparatus (CTA). Analytes verification was performed by head group analysis in MS/MS experiments. In a

multimodal imaging approach in the same sample elemental distribution was visualized without matrix

removal by means of µ-XRF spectrometry (Atominstitut).

Parts of this project were funded the PhD p og a MEIBio Mole ula a d Ele e tal I agi g i

Bios ie es p o ided the TU Wie . Autho s tha k Lau a To li so fo sha i g he e pe ie e du i g a

COST STSM in Vienna (COST Action BM1104).

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Platinum speciation analysis addressing metallodrug-protein interaction in

preclinical anticancer research

Luis Gálveza; Sarah Theinera; Christian Kowolb; Bernhard Kepplerb; Stephan Hannc; Gunda

Koellenspergera

a Institute of Analytical Chemistry, University of Vienna, Vienna, Austria

b Institute of Inorganic Chemistry, University of Vienna, Vienna, Austria

c Department of Chemistry, University of Natural Resources and Life Sciences - BOKU Vienna, Vienna,

Austria

Since the serendipity of cisplatin in 1965 by Rosenberg et al. [1] the development of metallodrugs,

especially Pt-based drugs, has become a topical cancer research theme. In this work, we focused on Pt(IV)

compounds, which act as prodrugs until reduction and release of the active Pt(II) compound [2], and we

designed analytical methods for a more detailed understanding of drug stability, drug-protein interaction

and drug metabolism. Drug-protein interactions can have significant impact on the metabolism of the drug

and hence they have to be investigated in early stages of preclinical anticancer drug development. For this

purpose 3 different methods were compared: Size Exclusion Chromatography (SEC), cut-off filtration and

Turbo Flow Chromatography (TFC) in ex vivo studies.

References

[1] Rosenberg B., Van Camp L., Krigas T., Nature, 205(4972), (1965) 698-699.

[2] Pichler V. et al., Chem. Commun. (Camb)., 49(22), (2013) 2249-2251.

12th


Inhibition-based Human Monoamine Oxidase B Biosensors for the Determination

of MAO B Inhibitors

Maximilian Aignera, Kurt Kalcherb, Peter Macherouxc, Patricia Preisseggera, Astrid Ortnera

aInstitute of Pharmaceutical Sciences, University of Graz, Graz, Austria

bInstitute of Chemistry, University of Graz, Graz, Austria

cInstitute of Biochemistry, Technical University of Graz, Graz, Austria

Biogenic amines (BAs), including the catecholamines dopamine, epinephrine and norepinephrine, as well

as serotonin and phenylethylamine have numerous physiological functions in the human body.

Monoamine oxidases such as monoamine oxidase A (MAO A) and B (MAO B) are responsible for the

regulation of these amines. Increased and decreased levels of BAs are linked to different diseases like

dep essio , pho ia, Pa ki so s disease, pheo h o o to a a d eu o lasto a [ -4]. Therefore the

development of analytical devices for the determination of monoamines shows important areas of

application including the use as potential diagnostic and research tools (post mortem analysis) for the

above mentioned diseases. Another field of application is the determination of MAO inhibitors as the

enzyme acts as target for the treatment of certain monoamine related diseases.

The aim of this work was to develop a biosensor capable of the determination and characterisation of

MAO B inhibitors.

The presented sensor uses human monoamine oxidase B (hMAO B) as biological recognition element. The

enzyme is immobilised via a dialysis membrane on a 20 % MnO2 modified screen printed carbon working

electrode, acting as the transducer. The biosensor was validated and successfully tested for the

determination of selegiline (MAO inhibitor) in a finished medicinal product sample.

References

[1] Youdim M., Edmondson D., Tipton K., Neuroscience, 7(4), (2006) 295-309.

[2] Grünwald F., Ezziddin S., Semin. Nucl. Med., 40(2), (2010) 153-163.

[3] Youdim M., Gross A., Finberg J., Brit. J. Pharmacol., 132(2), (2001) 500-506.

[4] Thomas D., Taylor J., Barnaby O., Hage D., Clin. Chim. Acta, 398(1-2), (2008) 63-69.

35 10th

- 11th


Session IV - Health II

Chair: Stefan Tanda

Saturday 11th

June 2016, 10:40 - 12:00

12th


Combination of FTIR and LA-ICP-MS micro-imaging techniques for the study of a

tumor treated with sunitinib and cisplatin

Anna Balbekova, Maximilian Bonta, Andreas Limbeck, Johannes Ofner, Bernhard Lendl

Institute of Chemical Technologies and Analytics, Vienna University of Technology, Vienna, Austria

In this work for the first time Fourier transform infrared (FTIR) micro-imaging, which provides molecular

information, and laser ablation inductively coupled mass spectrometry (LA-ICP-MS) micro-imaging, which

gives access to elemental content of the same sample, were merged. The object of investigation in this

study is a tumor implanted in mice, which was treated by antitumor drugs (sunitinib, cisplatin). The aim of

our work is to visualize histologically relevant structures in the tumor by means of combined FTIR and LA-

ICP-MS images and to characterize biochemical changes induced by the drug treatment. Cryogenic

microtome cuts of a tumor were produced, which were deposited on a one-side polished silicon wafer.

Silicon was chosen because it is partly transparent in the mid-IR and only produces a small background in

the LA-ICP-MS measurements. Multivariate analysis of a hyperspectral FTIR image allowed discrimination

of dead and viable tumor areas which partially could not be revealed by a conventional histological

investigation. Spectra of tumor areas affected by drugs reveal changes in the secondary structure of

cellular proteins, i.e. an increase of beta sheet structures and a decrease of alpha helices compared to the

viable tumor. LA-ICP-MS imaging accompanying this biochemical analysis provided information about the

distribution of applied drugs as well as the distribution of non-organic elements within the tumor which

correlates with the results of FTIR analysis. Thus, analysis of the combined images obtained with different

techniques, analogously to [1], gave the possibility to correlate information from different datasets. It

allowed us to deepen the understanding on the effects of antitumor treatment by the antitumor drugs.

References

[1] Ofner, et. al., Anal. Chem., 87 (18), (2015) 9413-9420.

37 10th

- 11th


Towards the development of a LC-MS/MS multi-method for the quantification of

mycotoxins in human breast milk

Dominik Braun, Benedikt Warth, Doris Marko

University of Vienna, Department of Food Chemistry and Toxicology, Vienna, Austria

Crops are frequently contaminated by mycotoxins, which are secondary metabolites of molds. The

aflatoxins (AFs), fumonisins (FBs), zearalenone (ZEN), ochratoxin A (OTA) and deoxynivalenol (DON) are of

particular concern, due to their toxicity and frequency of occurrence. Various disorders and diseases have

been associated with these food contaminants, e.g. liver cancer, immunomodulation, kidney toxicity,

stunting and endocrine changes [1, 2].

Human breast milk is perceived to be typically safe, and the World Health Organization recommended to

exclusively breastfeed for at least 6 months [3, 4]. Nevertheless, mycotoxins may be transferred to human

breast milk and can create an imbalance in the benefits-risk-ratio. In contrast to breast milk,

complementary and weaning food is strictly regulated in the EU without any clearly established risk

characterization for mycotoxins.

To ensure the safety and quality of breastfeeding, accurate and valid measurements are required. Based

on these needs, first steps towards the development of a new LC-ESI-MS/MS method for the simultaneous

quantification of mycotoxins including the parent compounds (AFs, OTA, ZEN, FBs, DON and NIV) and

some selected phase I eta olites α-)ea ale ol a d β-Zearalenol) have been applied.

Preliminary data of first examples as well as sample preparation procedures of human breast milk will be

presented.

References

[1] Bennett, J. W., Klich, M., Clin. Microbiol. Rev., 16, (2003) 497-516.

[2] Turner, P. C.et al. Nutr. Res. Rev., 25, (2012) 162-179.

[3] World Health Organization (WHO), Horta, B. L. (2007). Evidence on the long-term effects of

breastfeeding: WHO Geneva.

[4] World Health Organization WHO, (2015). Infant and young child feeding. Fact sheet No.342.

Available at: http://www.who.int/mediacentre/factsheets/fs342/en/.

12th


Analytical method development for selenoneine using model compounds

Nina Kroepfl, Doris Kuehnelt, Kevin A. Francesconi

Institute of Chemistry – Analytical Chemistry, University of Graz, Graz, Austria

Selenium is an essential trace element important for human health because of its role in several enzymes

and its many purported nutritional benefits. The health benefits associated with selenium are likely

determined in part by the form of selenium ingested. Although most foods contain selenium in protein-

bound forms, as selenomethioneine or selenocysteine, marine fish contain an unusual histidine derivative,

namely 2-selenyl-Nα, Nα, Nα-trimethyl-L-histidine (selenoneine) as the major water-extractable selenium

form.[1] The recent reported presence of selenoneine in human blood and its proposed antioxidant

activity have generated increased interest in the human metabolism of this selenium species.[1-3] Such

research has necessitated an analytical method for the quantitative measurement of selenoneine in food

and in human bodily fluids.

The determination of selenoneine, however, poses many difficulties. There is currently no standard of

selenoneine available (a synthesis is underway by our group in parallel with the analytical component) to

be used in the development of the analytical method. Additionally, unlike its sulfur analogue

ergothioneine, which is stable at physiological conditions in its thione form, selenoneine is readily auto-

oxidized due to its reactive selenol-group and forms dimers. To overcome this latter problem, a

derivatization procedure has been investigated to convert selenoneine into a defined and stable form

thereby ensuring reliable quantitative results for its determination. Preliminary results from this approach

are presented together with future analytical steps and an outline of the proposed application of the

technique to samples relevant to human metabolism and health.

References

[1] Yamashita Y., Yamashita M., J. Biol. Chem., 285, (2010) 18134-18138.

[2] Klein M., Ouerdane L., Bueno M., Pannier F., Metallomics., 3, (2011) 513-520.

[3] Yamashita M., Yamashita Y., Ando T., Wakamiya J., Akiba S., Biol. Trace Elem. Res. 156, (2013) 36-44.

39 10th

- 11th


Arsenic Species in Human Milk

Michael Stibollera, Georg Rabera, Elin Lovise Folven Gjengedalc, Merete Eggesbøb and Kevin A.

Francesconia

a Institute of Chemistry-Analytical Chemistry, NAWI Graz, University of Graz, Graz, Austria

b Norwegian Institute of Public Health, Oslo, Norway

c Norwegian University of Life Sciences, Ås, Norway

The toxicity of arsenic depends on its chemical form. Inorganic arsenic is highly toxic to humans whereas

organic arsenic compounds are generally considered as much less toxic. Risk assessment of arsenic

exposure must therefore consider the type of arsenic compound, but few studies exist so far.

Furthermore, risk assessments must include studies on the most vulnerable within a population such as

newborns and infants, thus estimation of these species in human milk is needed. Such assessments require

sensitive and robust methods for the determination of arsenic species. Herein we report a method for the

determination of arsenic species at low concentrations in human milk by high performance liquid

chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICPMS). The method

incorporates a protein precipitation step with trifluoroacetic acid followed by addition of an organic

solvent for phase separation and fractionation of arsenic species. The aqueous phase was subjected to

cation-exchange and anion-exchange chromatography with aqueous pyridine and ammonium bicarbonate

buffer solutions as mobile phases, respectively. For method validation, human milk and an infant milk

formula were spiked with defined amounts of dimethylarsinate, methylarsonate, arsenate and

arsenobetaine. The proposed method was applied to 51 human milk samples from the Norwegian NoMIC

study conducted by the Norwegian Institute of Public Health. We report total arsenic and arsenic

speciation data obtained in this study.

12th


Session V - Metabolomics

Chair: Simone Braeuer

Saturday 11th

June 2016, 12:30 - 14:10

41 10th

- 11th


Elucidating the fungal attack of Fusarium graminearum against wheat: insights

from a metabolomics time series experiment

Alexandra Simadera, Alexandra Paricha, Michael Sulyoka, Manuel Hoferb, Maria Dopplera,

Christoph Bueschla, Barbara Steinerb, Marc Lemmensb, Hermann Buerstmayrb, Gerhard Adamc,

Justyna Rechthalerd, Rudolf Krskaa, Rainer Schuhmachera

a Center for Analytical Chemistry, Dept. of Agrobiotechnology (IFA-Tulln), University of Natural Resources

and Life Sciences - BOKU Vienna, Tulln, Austria

b Institute for Biotechnology in Plant Production, Dept. of Agrobiotechnology (IFA-Tulln), University of

Natural Resources and Life Sciences - BOKU Vienna, Tulln, Austria

c Institute of Applied Genetics and Cell Biology, University of Natural Resources and Life Sciences - BOKU

Vienna, Tulln, Austria

d University of Applied Sciences Wr. Neustadt-Campus Tulln, Tulln, Austria

The plant disease Fusarium head blight (FHB) causes severe yield and quality losses in wheat. In order to

develop strategies against FHB, studying the interaction between the pathogen Fusarium graminearum

(Fg) and its host plant is of great benefit.

For this reason, a metabolomics experiment comparing two near isogenic wheat lines differing in

resistance QTLs Fhb1 and Qfhs.ifa-5A were performed. Samples of the resistant and the susceptible lines

were inoculated with Fg and harvested at 0, 3, 6, 12, 24, 36, 48, 72, 96 hours after treatment in order to

investigate changes in the metabolome over time. Targeted GC-MS and LC-MS analysis, which comprise

primary and secondary metabolism, provided a holistic view in the metabolome. Complement

transcriptomic data served as reference for the fungal biomass. To investigate the fungal attack,

metabolomics time course data for Fg secondary metabolites and putative fungal biomarker compounds

(e.g. mannitol, arabitol, xylitol) were studied. Fusarium specific metabolites could be detected as early as

24-36 hours after inoculation. Time course of their formation has been investigated in detail which mostly

revealed higher abundances of Fg metabolites in the resistant genotype at earlier time points, whereas at

later time points the fungal metabolites were more abundant in the susceptible line.

12th


Combining tracer based and global stable isotopic labeling for untargeted

metabolomics of Fusarium head blight on wheat

Maria Dopplera1, Bernhard Klugera1, Christoph Büschla1, Alexandra Simadera1, Justyna

Rechthalerb, Marc Lemmensa2, Gerhard Adamc, Rainer Schuhmachera1

a Department of Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences - BOKU

Vienna, Vienna, Austria; 1 Center for Analytical Chemistry, 2 Institute of Biotechnology in Plant Production

b University of Applied Sciences Wr. Neustadt, Campus Tulln, Tulln, Austria

c Institute of Applied Genetics and Cell Biology, University of Natural Resources and Life Sciences - BOKU

Vienna, Tulln, Austria

In untargeted metabolomics, identification of metabolites is known as a major bottleneck. Application of

stable isotopic labeling (SIL) gives numerous advantages like separation of biological from non-biological

data or the proper assignment of the number of carbon atoms of each detected metabolite. In this work, a

tracer based and a global SIL approach were combined to study the effect of the Fusarium graminearum

virulence factor deoxynivalenol (DON) on wheat metabolism. To this end, the two endogenous 13C-labeled

tracers 13C-phenylalanine and 13C-tryptophan were applied on flowering wheat ears in absence and

presence of the mycotoxin DON to follow their biotransformation. In addition, fully labeled 13C and native

wheat plants were investigated for further metabolite response of all Phe- and Trp-derived wheat

metabolites upon treatment with DON. Samples were milled, extracted and analyzed by LC-HRMS with an

Exactive plus Orbitrap instrument and polarity switching. Preliminary data evaluation resulted in the

detection of hundreds of Phe- and Trp-derived metabolites and about 1000 metabolites in the global

labeled samples. Database search showed that some detected metabolites are already known to be

involved in plant defense reactions. This approach allowed assigning Phe- and Trp-derived metabolites to

distinct structure classes. Differential analysis of metabolite abundances allowed identification of several

defense related metabolites, which are directly affected by treatment with DON. Combination of global

and tracer based SIL approaches proved to be promising in order to characterize unknown compounds,

which usually represent more than 75 % of all detected metabolites in untargeted metabolomics

approaches.

43 10th

- 11th


Anion-exchange chromatography coupled to high resolution mass spectrometry in

metabolomics

Michaela Schwaigera, Máté Rusza, Yasin El Abieada, Evelyn Ramplera, Gunda Koellenspergera

a Institute of Analytical Chemistry, University of Vienna, Vienna, Austria

The analysis of metabolites is challenged by very polar and especially charged metabolites. Both reversed-

phase and hydrophilic interaction liquid chromatography provide some retention but also have some

severe drawbacks regarding the separation of these metabolites. Moreover, phosphorylated compounds

such as nucleotides strongly interact with any stainless steel present in the system used for analysis. As

these compounds are of high importance in different fields, anion-exchange chromatography represents

an alternative for charged metabolites.

We explore the potential of ion exchange chromatography in combination with high resolution mass

spectrometry for targeted and non-targeted metabolomics. Analytical figures of merit will be presented

for nucleotides, sugar phosphates and organic acids.

Furthermore, high resolution Orbitrap mass spectrometry is successfully used for quantification.

Finally, the method is applied to an in vitro cancer cell study investigating the differences between a

resistant and sensitive cancer cell line.

12th


U targeted Meta olo i s of Bor eo s E plodi g A ts

Michaela Fischera, Alexandra Paricha, Alexandra M. Simadera, Alexey G. Kopchinskiyb, Herbert

Zettelc, Alice Lacinyc, Carina Pretzerb, Rahimi Mohammadjavadb, Kamariah A. Salimd, Irina S.

Druzhininab and Rainer Schuhmachera

a Center for Analytical Chemistry, University of Natural Resources and Life Sciences - BOKU Vienna, IFA-

Tulln, Tulln, Austria

b Institute of Chemical Engineering, University of Technology, Vienna, Austria

c Natural History Museum Vienna, Vienna, Austria

b Environmental and Life Sciences, Universiti Brunei Darussalam, Brunei Darussalam

To kill an enemy, ants of the Colobopsis cylindrica (COCY) complex living in the rain forest of Borneo

sacrifice themselves by rupturing their gaster to release a sticky and irritant secretion from their

hypertrophied mandibular glands. It is hypothesized that the investigated ants use this gland content not

only for defense, but also for nest hygiene to protect their own microbiome from foreign microbes. Firstly,

GC-MS with the use of either HS-SPME or liquid injection as sample introduction technique was used to

reveal the chemical composition of this secretion. More than 55 substances, mainly belonging to the

structure classes of alkanes, alkenes, terpenoids, carboxylic acids, ketones and phenols, were annotated or

identified. The reported antimicrobial and antifungal effects of some of the identified compounds support

the hypothesis that the ant secretion indeed acts against potentially invading microorganisms.

Secondly, to reveal the mechanism used by ants to discriminate between nestmates and enemies, we

applied liquid injection GC-MS to investigate the cuticular hydrocarbon (CHC) profiles of different species

and castes of the COCY complex. The profiles differed between all investigated ant species and also

between workers and reproductives of the same colony. Interestingly, in pilot behavior experiments in

which pure CHC extracts were offered to COCY ants, they only showed aggressive behavior when they

sensed non-nestmate CHCs. Our study thereby demonstrates that COCY ants are capable of discriminating

between non-nestmates and nestmates via their cuticular hydrocarbon profiles.

45 10th

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Challenges in targeted metabolomics – a comparison of capillary GC and LC triple

quadrupole MS

Benedikt Putz, Gregor Mikl, Peter Suralik, Günter Allmaier, Martina Marchetti-Deschmann

Institute of Chemical Technologies and Analytics, TU Wien, Vienna, Austria

Usually an analytical method is optimized for a small set of analytes having similar physico-chemical

properties. Such methods can usually not optimally be used for a broader array of analytes as present in a

complex biological matrix. The huge variety of metabolic analytes resulted in the application of many

different techniques, methods and analytical strategies finally suitable for metabolomics. Two high

performance chromatographic methods, both in combination with triple quadrupole mass spectrometry

applying low energy CID, were used for the quantification of representative metabolites of the primary

carbon cycle, namely capillary GC-EI-MS/MS and LC-ESI-MS/MS. Quantification was carried out by multiple

reaction monitoring (MRM) which allowed very sensitive and selective analysis. For GC-EI-MS/MS,

metabolites have to be derivatized because of poor volatility. Methoximation with methoxyamine

hydrochloride in pyridine followed by trimethyl silylation with N-methyl-N-(trimethylsilyl)-

trifluoroacetamide (MSTFA) showed high efficiency although multiple derivatives were observed for

several substances. Compared to the high separation efficiency of GC on a Zebron ZB 50 column, HILIC

(hydrophobic interaction LC) on an NH2 column using a basic water/acetonitrile gradient showed poor

selectivity for the analytes of interest. Yet, no sophisticated sample preparation is needed. For both

methods MRM detection allowed to reach low LODs.

Overall it can be said that each methodology favored certain analytes allowing for sensitive quantification

in biological samples. Yet, derivatization within the sample preparation makes GC-EI-MRM analysis more

vulnerable to errors than the LC-ESI-MRM method.

Acknowledgement: We gratefully thank Shimadzu Austria for supporting this work by the loan of the

TQ8040 and the LCMS8030+ to the Metabolomic and Bioprocess Analytics Laboratory.

12th


Session VI - Food

Chair: Oliver Steiner

Saturday 11th

June 2016, 14:10 - 15:50

47 10th

- 11th


Identification of odor active NIAS (non-intentionally added substances) in food

contact material

Brigitte Jaksa, Erich Leitner

Institute of Analytical Chemistry und Food Chemistry, Technical University Graz, Graz, Austria

Beside all the classical packaging parameters like physical parameters, printability, etc. packaging for

sensitive applications must fit additional requirements. Especially the packaging of sensitive goods (food

stuff, pet food, sanitary and cosmetic products, pharmaceutical and medical products, toys for kids and

a ies, te tiles, to a o p odu ts… eeds a lea u de sta di g of the i te a tio s et ee the

packaging and the packed good to guarantee the quality and to ensure the legal requirements.

Unknown substances can enter the process chain and must be identified and quantified to ensure the

product quality. Non-Intentionally Added Substances (NIAS - as defined in the Regulation (EC) No. 10/2011

[1] – plastic implementation measure) originate from break-down products of food contact materials,

impurities of starting materials, unwanted side-products and various contaminants from recycling

processes [2].

This presentation deals with the strategies for the identification of odor active NIAS in different food

contact materials.

Only the combination of different techniques like Gas Chromatography-Olfactometry (GCO), Gas

Chromatography with different detectors (MS, FID, NPD, FPD...), multidimensional GC (MDGC & GCxGC)

and the use of Retention Indices ensure a correct identification.

With several real world samples the application of these techniques will be demonstrated. Difficulties that

may arise in the data-interpretation process and approaches to resolve them will be discussed.

References

[1] COMMISSION REGULATION (EU) No 10/2011 of 14 January 2011 on plastic materials and articles

intended to come into contact with food.

[2] http://www.foodpackagingforum.org/food-packaging-health/non-intentionally-added-substances-nias.

12th


Closer looking to Mineral Oil Hydrocarbons (MOSH/MOAH) in paper packaging

used for food contact

Andrea Jurek, Erich Leitner

Institute of Analytical Chemistry and Food Chemistry, Technical University of Graz, Graz, Austria

A currently heavily discussed theme concerns saturated (MOSH) and aromatic mineral oil hydrocarbons

(MOAH) in food and packaging materials. MOSH consist of linear and branched alkanes, and alkyl

substituted cycloalkanes, whilst MOAH include mainly alkyl-substituted polyaromatic hydrocarbons with

up to four aromatic rings. The main focus is on the aromatic fraction, which is suspected to include

potential carcinogenic and mutagenic constituents. Most data on mineral oil in food and food packaging

material were generated by on-line or off-line coupled high performance liquid chromatography-gas

chromatography-flame ionization detection (HPLC-GC-FID), determining the total concentration of MOSH

and MOAH. Because of FID detection, which is necessary for the quantification of MOSH and MOAH, as it

is the only detection method which provides the same response per mass of hydrocarbons, there is a lack

of knowledge concerning the composition of the fractions. Besides these, it is not possible to resolve the

fractions into individual components for identification, as they form broad humps of unresolved

compounds.

However, using methods based on multidimensional gas chromatography as well as high resolution mass

spectrometry, it is possible to distinguish and identify certain MOAH sub-classes. This work focuses on the

aromatic fraction using different comprehensive GCxGC set-ups (columns of different polarity, variation in

the odulatio f e ue … a d GC-HR-MS for the identification of individual unknown components.

Furthermore, the impact on the separation performance and efficiency of the different set-ups was

considered.

49 10th

- 11th


Horseradish – a challenging method development

Valerian Kalb, Erich Leitner

Institute of Analytical Chemistry and Food Chemistry, Technical University of Graz, Graz, Austria

Horseradish (Armoracia rusticana) is used for centuries for traditional cuisine. The styrian area is the

second largest cultivation area in Europe, with an annual production of 3 738 tones (325 ha acreage) of

horseradish [1].

The distinctive aroma of horseradish is caused by mustard oils, which mainly belong to the group of

isothiocyanates. These isothiocyanates are stored in the cells in form of glucosinolates. When the cell is

damaged the spatial separation between precursor and enzyme is eliminated, which leads to the

breakdown of the glucosinolates by the cleavage enzyme myrosinase. The spicy, pungent lachrymating

(nasal trigeminal pain reaction) aroma derives primarily from allyl isothiocyanate, which makes up the

largest part of the volatile fraction (64-82 %) [2]. One quality attribute of horseradish products is their

pungency, which correlates with the amount of glucosinolates in the raw product, the enzymatic cleavage

conditions and the processing/storage of the product. Analytically accessible values are the glucosinolate

content, the enzymatic activity and the amount of breakdown products.

For the determination of allyl isothiocyanate a validated method based on liquid extraction with

dichloromethane and a subsequent analysis by GC-FID was developed. As allyl isothiocyanate tends to

hydrolyze fast under humid conditions and exhibits a high volatility, a specifically tuned preparation

procedure was required, also addressing matrix effects and the inhomogeneity of grated horseradish

products from the market. This validated method was used to make a market survey of different

commercial available products bought from local supermarkets.

References

[1] Bader R., Kreisel M., Statistik Austria (2015), 1-15.

[2] Tomsone L., Kruma Z., Galoburda R., Talou. T., Proceedings of the Latvia University of Agriculture. 29

(2013), 1-10.

12th


Fresh, juicy, “tyrian - The Flavor of the Old Apple Variet Ilzer ‘ose

Iris Taubera, Georg Innerhoferb, Barbara Siegmunda

a Institute of Analytical Chemistry and Food Chemistry, Technical University of Graz, Graz, Austria

b School for Fruit Growing & Viticulture Silberberg, Leibnitz, Austria

In Styria - the apple cultivation hot spot of Austria - about 80% of the Austrian apples are harvested. The

majority of the new apple varieties are cultivated by plantation growing, whereas old apple varieties grow

in so-called meadow orchards. These orchards represent an enormous pool of mainly old apple varieties.

Such varieties are currently produced without knowing their variety-specific characteristics.

The old apple a iet Ilze ‘ose is o e of these old apple varieties. The rather small, intense-red apples

with white flesh make it interesting for producers of high quality apple juice and or apple wine. The aim of

this stud as to ha a te ize the fla ou of Ilze ‘ose usi g oth ethods f o sensory as well as

instrumental-analytical techniques. It was the aim of this study to investigate the primary aroma

o pou ds of Ilze ‘ose . To e a le to fo us o p i a fla ou o pou ds, apple e z es e e

inactivated before the analysis.

The complete sensory characterisation was performed by using an expert panel of the intact as well as of

the sliced apples after enzyme inactivation.

For the investigation of the volatile compounds, extraction and enrichment of the volatile compounds

were carried out by using headspace solid-phase micro-extraction. For the identification of the volatile and

odour active compounds GC-MS as well as GC-olfactometry were applied. In GC-olfactometry, the human

noses of trained panellists were used as selective and sensitive detectors to identify the odour active

compounds. Detection frequency was used to identify the most potent odourants of this apple variety.

The o i atio of these te h i ues p o ides deep i sight i to the fla ou of the old apple a iet Ilze

‘ose .

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List of Participants

Name Email Institution

Maximilian Aigner KFU Graz [email protected]

Anna Balbekova TU Vienna [email protected]

Simone Braeuer KFU Graz [email protected]

Dominik Braun University of Vienna [email protected]

Markus Bruckner Bruckner Analysentechnik [email protected]

Wim Cuypers University of Vienna [email protected]

Maria Doppler IFA Tulln, BOKU [email protected]

Heiko Egenolf BASF [email protected]

Josef Ehgartner TU Graz [email protected]

Yasin El Abiead University of Vienna [email protected]

Lisa Emhofer JKU Linz [email protected]

Kathrin Ertl KFU Graz [email protected]

Lisa Fasshold KFU Graz [email protected]

Michaela Fischer IFA Tulln, BOKU [email protected]

Eva Fritzsche TU Graz [email protected]

Luis Galvez Montano University of Vienna [email protected]

Marko Grabarics University of Vienna [email protected]

Manfred Hambammer Messer AustriaGmbH [email protected]

Stephan Hann BOKU Vienna [email protected]

Junjian Hu BOKU Vienna [email protected]

Regina Huber Shimadzu HandelsgesmbH [email protected]

Gernot Hudin Agilent Technologies [email protected]

Brigitte Jaksa TU Graz [email protected]

Andrea Jurek TU Graz [email protected]

Valerian Kalb TU Graz [email protected]

Christian Klampfl JKU Linz [email protected]

Gunda Koellensperger University of Vienna [email protected]

Nina Kroepfl KFU Graz [email protected]

Si-Hung Le BOKU Vienna [email protected]

Wolfgang Lindner University of Vienna [email protected]

Leila Maringer JKU Linz [email protected]

12th


Florian Meischl University of Innsbruck [email protected]

Franz Mlynek AGES Linz [email protected]

Maria Moßhammer TU Graz [email protected]

Bernhard Mueller TU Graz [email protected]

Astrid Ortner KFU Graz [email protected]

Benedikt Putz TU Vienna [email protected]

Matthias Rainer University of Innsbruck [email protected]

Anna Rathgeb BOKU Vienna [email protected]

Hermann Rausch Agilent Technologies [email protected]

Mate Rusz University of Vienna [email protected]

Dieter Schemeth University of Innsbruck [email protected]

Rainer Schuhmacher IFA Tulln, BOKU [email protected]

Michaela Schwaiger University of Vienna [email protected]

Alexandra Simader IFA Tulln, BOKU [email protected]

Oliver Steiner KFU Graz [email protected]

Michael Stiboller KFU Graz [email protected]

Gerhard Stingeder BOKU Vienna [email protected]

Anastasiya Svirkova TU Vienna [email protected]

Stefan Tanda KFU Graz [email protected]

Iris Tauber TU Graz [email protected]

Christoph Walcher KFU Graz [email protected]

Franz Weigang Agilent Technologies [email protected]

Victor Weiss TU Vienna [email protected]

Andrea Zenker Agilent Technologies [email protected]

Samuele Zoratto TU Vienna [email protected]

53 10th

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– NOTES –

Documents

static.uni-graz.at2016/06/11 · 10 th - 11 June 2016, University of Graz 9 Foreword Dear Collegues and Students, it is our pleasure to welcome you at the 12th ASAC JunganalytikerInnenforum