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Table of Contents 2017 MCF Spring Symposium
Abstracts for Oral Presentations
Table of Contents
KEYNOTE PRESENTATION ............................................................................................................. 3
Exploration of Martian Habitability with the Curiosity Rover ....................................... 3
Paul R. Mahaffy, PhD ............................................................................................... 3
Environmental Sessions: ......................................................................................................................... 4
Towards Direct Monitoring of VOCs from Aqueous Solutions: A 20 Year Crusade
with Undergraduate Students .......................................................................................... 4
tony Borgerding ......................................................................................................... 4
Analysis of Volatiles in Food Packaging Paper Board Using Itex Dynamic Headspace 5
Edward Koleski ......................................................................................................... 5
Increasing Reproducibility in the Analysis of Semi Volatile Contaminates Monitored
in Water Samples for Analysis by EPA Method 8270d ................................................. 6
Vanessa Abercrombie ............................................................................................... 6
A Sensitive Method for Analyzing 1,4-Dioxane in Minnesota Waters .......................... 7
Colleen Detloff, Katie Rinker ................................................................................... 7
Automated Sampling of Methanol Extractions for USEPA Method 8260 and USEPA
Method 5030 ................................................................................................................... 8
Anne Jurek ................................................................................................................. 8
Chromatography Methods for Efficient Characterization of Lignin Molecular Weight
Distribution ..................................................................................................................... 9
Anastasia Andrianova, Natallia Yeudakimenka, Sam Lilak, Evguenii Kozliak,
Alena Kubátová ......................................................................................................... 9
Aqueous Resistant GsBP-Wax/Aq Columns ................................................................ 10
Zoe Wang ................................................................................................................ 10
CLINICAL/BIOMARKERS SESSIONS:...................................................................................... 11
Protein Mass Spectrometry: Replacing Ambiguity with Clarity in the Clinical
Laboratory ..................................................................................................................... 11
Robert Bergen ......................................................................................................... 11
Analytical Challenges of Steroids and Steroid Metabolites ......................................... 12
Jolaine Hines ........................................................................................................... 12
Anodyne by Design: Detecting the Use of Clandestine, Designer Opiates .................. 13
Gregory C. Janis ...................................................................................................... 13
Combining Low and High Probability Isotopes as a Tool Extending the Dynamic
Range of LC-MS/MS Assays ....................................................................................... 14
Table of Contents 2017 MCF Spring Symposium
Melissa M. Goggin, Anna M. Miller, An Nguyen, Stephanie D. Gozum, and
Gregory C. Janis ...................................................................................................... 14
Simple and Sensitive Dilute-and-Shoot Determination of Plasma Carotenoids by
LCMS ............................................................................................................................ 15
Keith Voeller1, Brady Roemmich
2, Lisa Jahns
1, Michael R. Bukowski
1,2 .............. 15
Development of Analysis Method(s) for Biomarker Correlation to Sulfur Mustard
Dose .............................................................................................................................. 16
Erica Manandhar, Adam Pay, Livia Veress and Brian A. Logue ........................... 16
Comparative Evaluation of Mass Spectrometry Platforms for Lipidomic Analysis .... 17
Marzieh Ramezani, Edgar A. Arriaga ..................................................................... 17
FOOD SAFETY SESSIONS: ............................................................................................................ 18
The Analysis of Polar Ionic Pesticides by Ion-Exchange Chromatography Tandem
Mass Spectrometry: The Possible Solution to a Longstanding Problematic Analysis? 18
Jonathan Beck,(3) Richard J. Fussell,(1) Stuart Adams,(2) Jonathan Guest,(2)
Michael Dickinson,(2) and Frans Schoutsen(4) ...................................................... 18
Extraction and Analysis of Organochlorine Pesticide Residues in Fatty Matrix by
Enhanced Matrix Removal-Lipid and GC/MSMS ....................................................... 19
Joan Stevens ............................................................................................................ 19
LC INNOVATION SESSIONS: ....................................................................................................... 20
Improve HPLC Separations by Carefully Matching Column Pore-Size to Solute-Size20
Richard A. Henry .................................................................................................... 20
Impacts of Ligand Structure On Protein Binding: Performance of Ion-Exchange
Membranes .................................................................................................................... 21
Jerald K. Rasmussen, .............................................................................................. 21
Cathy A. Bothof, Semra Colak Atan, Robert Fitzsimons, George Griesgraber,
Federica Sgolastra, Andrew Vail ............................................................................ 21
GC INNOVATION SESSIONS: ...................................................................................................... 22
Quantitative Carbon Detector for Calibration-Free Quantification of Complex
Mixtures ........................................................................................................................ 22
Professor Paul J. Dauenhauer .................................................................................. 22
Simultaneous Compound Identification and Quantification with Parallel Polyarc/FID
and MS .......................................................................................................................... 23
Charlie Spanjers ...................................................................................................... 23
Keynote Presentation 2017 MCF Spring Symposium
KEYNOTE PRESENTATION
EXPLORATION OF MARTIAN HABITABILITY
WITH THE CURIOSITY ROVER
PAUL R. MAHAFFY, PhD
Director - Solar System Exploration Division
NASA Goddard Space Flight Center
The Curiosity Rover has been on the surface of Mars for more than 4 years exploring the
geology and chemistry of what was once a large lake billions of years ago. The goal of the
mission is to understand the habitability of Mars, especially that of the ancient environment.
Could microbial life have existed in this environment? The Sample Analysis at Mars (SAM)
investigation of this rover conducts volatile and isotope measurements of both the atmosphere
and solids to help elucidate ancient environmental conditions and the global changes that have
transformed Mars over time. Chromatography is important for the search for organic compounds
in rocks with SAM’s gas chromatograph mass spectrometer experiment. Key measurements from
SAM, to date, include the first in situ detection of organics preserved in these rocks for billions
of years, the first in situ exposure age and K/Ar rock formation age, detection of perchlorates in
rocks and soils, measurement of the D/H ration of water that formed clays more than 3 billion
years ago, and detection of methane in the atmosphere. The Curiosity Rover is presently on the
flanks of Mt. Sharp and headed toward distinct clay and sulfate rich layers higher up on this
central mound in Gale crater. These and other ongoing exciting discoveries from the mission will
be described.
Paul Mahaffy is the Director of the Solar System Exploration Division at NASA Goddard Space
Flight Center. He has participated for many years at Goddard Space Flight Center in the study of
planetary atmospheres and the development of space qualified instrumentation. His main
research interests are: (1) Planetary science, especially chemical and isotopic composition of
planetary atmospheres and comets, (2) Advanced instrument development for organic and light
isotope analysis in planetary targets, and (3) Analog studies for martian and cometary materials
including both laboratory and field work.
Dr. Mahaffy is the Principal investigator (PI) on the Sample Analysis at Mars instrument Suite
on the Curiosity Rover that is currently operating on the surface of Mars. He is also PI on the
Neutral Gas and Ion Mass Spectrometer on the MAVEN Mars orbiter mission on its way to Mars
and the PI on the Neutral Mass Spectrometer on the LADEE mission that recently finished a very
successful mission in lunar orbit exploring the tenuous lunar exosphere. One of his past career
highlights was studying the atmosphere of Jupiter using data from a mass spectrometer on the
Galileo Probe as it parachuted down into that atmosphere and sent its data back to Earth.
Environmental Sessions 2017 MCF Spring Symposium
ENVIRONMENTAL SESSIONS:
***** PALMER AWARDEE *****
Abstract #1
TOWARDS DIRECT MONITORING OF VOCs
FROM AQUEOUS SOLUTIONS:
A 20 YEAR CRUSADE WITH UNDERGRADUATE STUDENTS
TONY BORGERDING
University of St. Thomas
St. Paul, MN
Analysis of volatile organic compounds (VOCs) is obviously well within the realm of gas
chromatography. However, the time required for chromatographic analysis makes it less
compatible with continuous monitoring of processes involving VOCs where
measurements need to be made in a time span of a minute or less.
This presentation will discuss studies we have undertaken for online extraction of VOCs
directly from solution into a GC or other instrument, culminating with the use of
microdialysis. There have been many challenges interfacing this gas-phase VOC extract
in a manner that is efficient in terms of time, sensitivity, and providing an injection
bandwidth that allows fast GC analysis. Results from experiments involving valve
injection, cryofocusing, novel stationary phases, and selective detectors that bypass the
GC column will be presented.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #14
ANALYSIS OF VOLATILES IN FOOD PACKAGING PAPER BOARD
USING ITEX DYNAMIC HEADSPACE
EDWARD KOLESKI
Aspen Research Corporation
Maple Grove, MN
The analysis of volatile organic compounds in food packaging paper board is important
for food safety. This analysis is typically conducted using headspace techniques in
conjunction with gas chromatography-mass spectrometry to achieve acceptable
sensitivities. The ITEX Dynamic Headspace uses a micro trap filled with an adsorbent
material to efficiently extract and concentrate compounds. The objective of this work was
to evaluate if the ITEX Dynamic Headspace can be used to effectively analyze for
volatile organics in packaging paper board, increase efficiency by reducing the analyst’s
time involved. Presented will be the data for eleven different volatile organic compounds
that were used to evaluate the ability of the ITEX Dynamic Headspace technique.
Different cardboard samples were analyzed. All the analyses were conducted using a GC-
MS. The extraction efficiency, reproducibility, and accuracy will be compared to the
standard headspace technique used for this analysis.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #13
INCREASING REPRODUCIBILITY
IN THE ANALYSIS OF SEMI VOLATILE CONTAMINATES
MONITORED IN WATER SAMPLES
FOR ANALYSIS BY EPA METHOD 8270D
VANESSA ABERCROMBIE
Agilent Technologies
The analysis of water sources for contaminates has become an important area for
environmental analysis. Volatile and semi volatile compounds, monitored under US-EPA
Method 8270, can be challenging to analyze because they differ greatly in boiling points
as well as chemical activity. Agilent's Ultra inert Flow Path, including DB-UI 8270D
columns and Ultra inert liners are designed to be rugged in the testing of these
problematic compounds. The use of the Intuvo 9000 GC for analysis of semi volatile
organic compounds further aids in the analysis of these active compounds. A guard chip,
a piece of "Metal Microfluidic Technology" has approximately 0.7 meters of path length,
is used instead of a traditional guard column, and is easy and fast to replace. The Intuvo
9000 GC also allows for ramping the temperature of the guard chip independently from
the inlet and oven. Ramping the guard chip ensures that all of the semi volatile analytes
do not get trapped on the guard chip, helps to keep the system clean, and decreases
injection to injection variation. The use of the Intuvo 9000 GC with the Ultra inert Flow
Path decreases injection variability due to active compounds, makes it easier to control
the system cleanliness, and has less downtime due to maintenance.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #5
A SENSITIVE METHOD FOR ANALYZING 1,4-DIOXANE
IN MINNESOTA WATERS
COLLEEN DETLOFF,
KATIE RINKER
Minnesota Department of Health
1,4-Dioxane is a cyclic di-ether that is used as an industrial solvent and as a chlorinated
solvent stabilizer. Due to its miscibility with water, 1,4-dioxane is highly mobile in
groundwater and can be found at the leading edge of contaminant plumes. 1,4-dioxane is
recalcitrant to abiotic and biotic degradation and it has a low Henry’s law coefficient.
These properties cause 1,4-dioxane to be very persistent in the environment and difficult
to treat by conventional remediation techniques. The U.S. EPA has classified 1,4-dioxane
as a probably carcinogen based on laboratory animal studies and insufficient data from
human epidemiological studies. In 2010 the U.S. EPA released a drinking water health
advisory of 0.35 µg/L based on a 1 in 106 lifetime cancer risk. Additionally, in 2013 the
Minnesota Department of Health issued a health risk limit of 1 µg/L for 1,4-dioxane in
drinking water. An analytical method was developed in house based on EPA method 522
with modifications to increase throughput and reduce the materials used. Briefly, 100 mL
water samples are extracted on an activated-carbon phase and eluted with 25%
acetonitrile in dichloromethane to a final volume of 1mL. The extract is then analyzed by
GC-MS without further sample preparation. The detection and reporting limits of 1,4-
dioxane by this method are 0.016 and 0.050 µg/L, respectively. The whole-method
accuracy determined at 0.1 and 10 mg/L in an environmental-water samples (n = 5
replicates each) was 101 % for both spike levels with a precision of 3.5 and 0.92 relative
standard deviation, respectively. The laboratory has analyzed over 500 samples in the last
year and has successfully met the low reporting limit criteria needed to look for this
chemical in Minnesota waters.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #6
AUTOMATED SAMPLING OF METHANOL EXTRACTIONS
FOR USEPA METHOD 8260 and USEPA METHOD 5030
ANNE JUREK
EST Analytical
The United States Environmental Protection Agency (USEPA) Method 8260 is used in
order to ascertain volatile organic compounds in waters, soils and solid waste samples.
Often times, soil and solid waste samples are so highly contaminated the sample needs to
be dispersed in methanol. Sample collection for contaminated soils can be obtained in
two ways. One, dispersing a bulk soil sample into a 40ml vial and adding methanol in the
lab or two, sending pre-weighed vials with a septum sealed cap that already contains the
pre-requisite methanol out in the field for soil sampling. No matter how the soil sample is
dispersed in methanol, an aliquot of the methanol extract needs to be added to water and
purged using USEPA Method 5030. This application will investigate automated sampling
of methanol soil extractions.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #16
CHROMATOGRAPHY METHODS FOR EFFICIENT CHARACTERIZATION
OF LIGNIN MOLECULAR WEIGHT DISTRIBUTION
ANASTASIA ANDRIANOVA,
NATALLIA YEUDAKIMENKA, SAM LILAK, EVGUENII KOZLIAK,
ALENA KUBÁTOVÁ
University of North Dakota
Determination of the molecular weight (MW) distribution of lignin and its degradation
products is an essential task for evaluating lignin degradation efficacy. Size exclusion
chromatography (SEC) is known to be strongly affected by secondary interactions. To
minimize the undesired non-SEC effects, an appropriate choice of SEC hardware setup is
essential. We evaluated lignin separation efficiency by gel filtration (GFC), gel
permeation (GPC) and reversed phase high performance liquid chromatography columns
while using four sets of commercially available polymeric standards and several in-house
synthesized low-MW lignin structure model compounds. The separation by two of the
tested GFC and GPC columns was affected by the analyte functionalities skewing the
targeted size exclusion effect, and so these columns were deemed unsuitable. Yet, one of
the tested GPC columns with highly cross-linked porous polystyrene/divinylbenzene
matrix-based stationary phase (Agilent, PLgel) demonstrated the best performance
towards the separation of various polymeric standards regardless of their nature, as well
as towards low-MW lignin structure model compounds. The lignin MW was successfully
determined utilizing the PLgel 1000Å column and the obtained MW values were
supported by the matrix-assisted laser desorption/ionization (MALDI) results.
Furthermore, we achieved an effective electrospray ionization (ESI) of intact lignin in the
positive ESI mode and assessed its MW distribution through the mass spectrum
deconvolution. The obtained MW values were similar to those determined by MALDI
and SEC.
Environmental Sessions 2017 MCF Spring Symposium
Abstract #15
AQUEOUS RESISTANT GSBP-WAX/AQ COLUMNS
ZOE WANG
General Separation Technologies, Inc.
Polyethylene Glycol (PEG) based GC columns are widely used for analyses of solvents
and less volatile polar compounds of alcohols, acids, ketones, esters and other polar
molecules. Water in these samples interacts with PEG to generate active hydroxyl groups.
As a result, most commercially available PEG columns exhibit peak tailing and
continuous performance degradation including retention loss. We present a new
polyethylene glycol (PEG) based GC Column GsBP-Wax-AQ with improved aqueous
resistance with little column performance degradation through a few demonstrative
analyses of aqueous samples such as acids, ethylene glycol, wine and industrial
chemicals. The result of the repeating runs up to 200 injections over a week are
summarized to demonstrate water resistance of the column with little performance
degradation.
Clinical/Biomarkers 2017 MCF Spring Symposium
Clinical/Biomarkers Sessions:
Abstract #1
PROTEIN MASS SPECTROMETRY:
REPLACING AMBIGUITY WITH CLARITY IN THE CLINICAL
LABORATORY
ROBERT BERGEN
Mayo Clinic
Rochester, MN
It is surprising that in the 21st century there still exist clinical tests that provide
ambiguous or incomplete results to the clinician. In an effort to remedy this situation my
laboratory and others have been exploring ways to utilize mass spectrometry to provide
much needed clarity. Examples of how mass spectrometry has provided the clarity
needed to accurately diagnose disease will be illustrated.
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #10
ANALYTICAL CHALLENGES OF STEROIDS AND STEROID METABOLITES
JOLAINE HINES
Mayo Clinic
Rochester, MN
Steroids pose a unique challenge in clinical laboratory analysis. They share a common,
four-ring structure differing only in their functional groups. In fact, many steroids and
their metabolites may be near-isobaric or even isomeric in their mass, rendering mass
spectrometry inadequate at separating them. Fortunately, the hydrophobic properties of
steroids can be harnessed using reversed-phase, liquid chromatography to offer another
level of separation that mass spec cannot achieve alone. Here we discuss the properties of
steroids including hydrophobicity, conjugation, and isomeric relationships and how
hydrolysis and liquid chromatography paired with mass spec can be used to quickly and
effectively separate and quantitate 26 steroid metabolites including 12 with isomers. We
will also discuss the clinical importance of accurate steroid metabolite profiling in
adrenal diseases such as adrenocortical carcinoma.
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #2
ANODYNE BY DESIGN:
DETECTING THE USE OF CLANDESTINE, DESIGNER OPIATES
GREGORY C. JANIS
MedTox Laboratories
In an effort to combat opiate abuse, the use of prescribed opiates and opioids in pain
management has evolved tighter restrictions. While these changes have undoubtedly
reduced the prevalence of opiate abuse, they have also left a subset of individuals
searching for alternatives to satiate addictions or assuage other opiate seeking
motivations. Tighter opiate controls are postulated to contribute to the recent increase in
heroin use locally and throughout the USA. However, heroin is not the only powerful
black market opiate available. Multiple classes of designer opiates exist stemming from
basic academic research and drug development research, and each compound has the
potential for clandestinely applied structural permutations. Each of these designer opiates
possesses its own unique pharmacology and toxicology and reported abuse. Almost all of
the designer opiates are invisible to established drug testing methodologies. While there
have been multiple high profile reports of designer opiate tragedies, it is difficult to
assess the true prevalence of these drugs. We postulate that the subset of opiate abusing
individuals within a pain management setting may be early adopters of designer opiates,
and thereby may serve as early indicators of designer opiate trends. Thus, we set out to
determine the prevalence of designer opiates in a pain management setting. We first
analyzed seized materials and emergency medicine / autopsy samples to identify the most
prevalent designer opiates and their metabolic pathways. From that, rapid LC-MS/MS
screening procedures and triggered confirmation procedures were developed, validated,
and applied to samples from known opiate abusers. A high percentage of heroin users
were identified to also be knowingly or unknowingly exposed to various clandestinely
produced designer opiates
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #9
COMBINING LOW AND HIGH PROBABILITY ISOTOPES
AS A TOOL EXTENDING THE DYNAMIC RANGE OF LC-MS/MS ASSAYS
MELISSA M. GOGGIN,
ANNA M. MILLER, AN NGUYEN,
STEPHANIE D. GOZUM, and GREGORY C. JANIS
MedTox / Labcorp
Toxicology testing is faced with the dilemma of detecting the lowest possible levels of
toxins while at the same time being tasked with analyzing samples possessing levels at
concentrations tens of thousands times higher than the LLOQ. The wide breadth of
concentration exceeds the linear dynamic range of available instrumentation. In addition,
high analyte concentrations can deteriorate chromatographic peak shape, shift peak
retention time, and alter fragmentation ratios. Current strategies for measuring samples
possessing analyte concentrations in excess of the upper limit of linearity rely on sample
dilution and re-analysis, which may significantly delay reporting results. The dynamic
range of a quantitative LC-MS/MS assay for amphetamine and methamphetamine in
urine was extended to include higher concentrations by exploiting the natural, low
abundance isotopes of the targeted analytes. The assay monitors transitions targeting the
predominant isotopes of the analytes, as would be expected for a typical LC-MS/MS
method. These high sensitivity transitions are monitored to specifically target analyte
concentrations ranging from 5 to 5,000 ng/mL, characterizing the low end of the curve. In
addition, parallel transitions are monitored targeting the natural population of the
molecules containing two 13C atoms. With 10 carbons, 0.54% of methamphetamine
molecules will contain two 13C atoms. The stable yet reduced probability of molecules
containing two 13C atoms enables the assay to quantify higher concentrations of the
analytes at the expense of reduced sensitivity. The low sensitivity analysis of the
isotopologues quantifies over the concentration range of 5,000 to 100,000 ng/mL. By
targeting the low probability 13C isotopes many of the pitfalls typically encountered
when measuring analytes at high concentrations are avoided. The high sensitivity arm of
the assay is then combined with the low sensitivity isotopologue analysis to cover a
concentration range of 5 to 100,000 ng/mL.
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #3
SIMPLE AND SENSITIVE DILUTE-AND-SHOOT DETERMINATION
OF PLASMA CAROTENOIDS BY LCMS
KEITH VOELLER1,
BRADY ROEMMICH2, LISA JAHNS
1, MICHAEL R. BUKOWSKI
1,2
1) USDA-ARS Grand Forks Human Nutrition Research Center, Grand Forks, ND
2) University of North Dakota, Grand Forks, ND
Carotenoids are a class of isoprenoid molecules that are metabolic precursors to retinol or
Vitamin A, and primarily found in deeply colored fruits and vegetables. Consumption of
these foods leads to elevations in the plasma levels of these molecules, which makes their
measurement in plasma an excellent measure of dietary fruit and vegetable intake. We
demonstrate the detection of α-carotene, β-carotene, β-cryptoxanthin, lycopene and
lutein/zeaxanthin using 10 µL of plasma in a “dilute-and-shoot” method that minimizes
sample handling. Eschewing typical hexane extraction, plasma (10 µL) was injected into
methanol (990 µL) containing internal standard (rac-tocol, 0.8 µM final concentration)
and deproteinized by centrifugation before injection. Samples were analyzed on a YMC
C-30 column with a binary gradient mobile phase that started at 9:1 methanol water (20
mM ammonium acetate), ramping to 7:2:1 acetonitrile:dichloromethane:methanol (20mM
ammonium acetate, 0.3% acetic acid). Spike recovery experiments demonstrated between
95-110% recovery of all analytes. The method was further validated using all three levels
of the human plasma standard NIST SRM 968e. Measured values across all three levels
for total α-carotene, total β-carotene, and total lycopene were 3%, 11% and 22% higher,
respectively, than the reported values for this standard. The measured values for total β-
cryptoxanthin were significantly higher than the certified values (57%), while the
lutein/zeaxanthin was on average 10% lower. These differences are likely due to the
dilute-and-shoot sample preparation, which unlike the methods used by NIST, does not
rely on the extraction efficiency of the multiple carotenoids into hexane. This method
proved robust, running over 500 sample injections on the same guard column and
analytical column with minimal effect on retention time and peak shape. Moreover, this
method was adaptable to microscale samples obtained through use of hematocrit tubes.
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #11
DEVELOPMENT OF ANALYSIS METHOD(S)
FOR BIOMARKER CORRELATION TO SULFUR MUSTARD DOSE
ERICA MANANDHAR,
ADAM PAY, LIVIA VERESS AND BRIAN A. LOGUE
South Dakota State University
Bis(2-chloroethyl)sulfide, commonly known as sulfur mustard (HD), is the most
frequently used chemical weapon in modern history. Classified as a vesicant, HD is an
alkylating agent which rapidly reacts with nucleophiles, such as DNA, RNA, lipids,
peptides, and proteins, via an episulfonium ion intermediate. Current investigations are
underway which focus on understanding the inhalation toxicity of HD in order to develop
effective therapeutic interventions. However, in vivo exposure studies via inhalation are
limited by challenges in quantifying the actual respiratory dose. Therefore, in this report,
urine and plasma samples of exposed pigs were analyzed using ESI-LC-MS/MS for
biomarkers of HD exposure. Following analysis of the plasma of HD exposed swine,
bis(2-chloroethyl) sulfoxide (SMO) and 1,1’ - sulfonylbis-[2-S-(N-acetylcysteinyl)ethane
(SBSNAE) showed the most promise as HD biomarkers correlating to inhalation dose.
Both metabolites showed strong signals following HD exposure and were not detected in
pre-exposure plasma. Other HD metabolites, thiodiglycol (TDG), 1,1’-sulfonylbis-[2-
(methylsulfinyl) ethane] (SBMSE), 1-methylsulfinyl-2-[2-
(methylthio)ethylsulfonyl]ethane (MSMTESE), and 1,1’-sulfonylbis[2-
(methylthio)ethane] (SBMTE) were analyzed but not detected in the plasma.
Thiodiglycol sulfoxide (TDGO) was detected in exposed plasma, but its presence in pre-
exposed and blank plasma samples limits its use as an unequivocal marker for dose
correlation.
Clinical/Biomarkers 2017 MCF Spring Symposium
Abstract #12
COMPARATIVE EVALUATION OF MASS SPECTROMETRY PLATFORMS
FOR LIPIDOMIC ANALYSIS
MARZIEH RAMEZANI,
EDGAR A. ARRIAGA
University of Minnesota, Department of Chemistry
Lipids play essential roles in cellular functions including cell structure and organization,
mediating signaling pathways, and sorting of macromolecules. Lipids composition and
distribution play an important role in the control of biochemical processes. Despite their
importance, characterization of lipids has been a challenge due to their structural
diversity. We develop methodologies and instrumentation for untargeted analysis and
identification of lipids. Unique lipid species could potentially be used as biomarkers in
specific human diseases including cancer and neurodegeneration. In this study, we
compared high resolution mass spectrometers with regards to identification of lipids in
relevant biological systems. Specifically, this includes comparing the analytical
capabilities of Orbitrap and QTOF mass analyzers in the analysis of a complex biological
sample defined by post nuclear fraction of C2C12 cells (mouse myoblast cell line).
instruments were operated in positive and negative electrospray ionization (ESI) modes
using the MS full scan as well as MS/MS over a mass range of 100–1200 Da. Main
analytical parameters used in this comparison include the following: signal to noise ratio,
resolution, sensitivity, limit of detection, mass and spectral accuracy. Software
comparison to discover possible variation of the extracted information includes
MassLynx, Xcalibur, Progenesis QI, LipidSearch and XCMS online. The findings
indicate that selection of a platform will highly depend on the purpose of the study. The
selected mass spectrometry platform and optimized data analysis workflow were used to
study the lipidomics of C.elegans samples of different age. The goal of this study was to
identify candidate biomarkers of aging in lipid droplet fraction of C.elegans samples.
This study is the first to compare the performances of QTOF and Orbitrap type
instruments in the context of lipidomics. Strategies developed here could be further
applied to other human samples and model organisms.
Food Safety 2017 MCF Spring Symposium
Food Safety Sessions: Abstract #19
THE ANALYSIS OF POLAR IONIC PESTICIDES
BY ION-EXCHANGE CHROMATOGRAPHY TANDEM MASS
SPECTROMETRY: THE POSSIBLE SOLUTION TO A LONGSTANDING
PROBLEMATIC ANALYSIS?
JONATHAN BECK,(3)
RICHARD J. FUSSELL,(1) STUART ADAMS,(2)
JONATHAN GUEST,(2) MICHAEL DICKINSON,(2) AND FRANS SCHOUTSEN(4)
1) Thermo Fisher Scientific, Hemel Hempstead, UK;
2) Fera Science Ltd, Sand Hutton, York, YO41 1LZ, UK;
3) Thermo Fisher Scientific, San Jose, CA, US;
4) Thermo Fisher Scientific, Special Solutions Center, Dreieich, Germany
Polar ionic pesticides, such as glyphosate, perchlorate, chlorate and the like, often occur
as residues in food, but are not always included in pesticide monitoring programs, simply
because they are not ‘amenable’ to generic multi-residue methods. The introduction of
the Quick Polar Pesticides (QuPPe) Method by the European Reference Laboratory for
single residue methods (EURL-SRM) has enabled more laboratories to conduct analysis
for at least some of the polar pesticides. Still, the absence of a liquid partitioning step, or
clean-up step, results in ‘dirty extracts’ containing high concentrations of matrix co-
extractives. Thus, the separation and accurate quantification of analytes in QuPPe
extracts is challenging. In this presentation, we will present an alternative approach to
this analysis. The application of high resolution ion-exchange chromatography with high
capacity columns, coupled to a triple quadrupole mass spectrometer can overcome the
issues experienced with other chromatographic techniques. Using the IC-MS/MS
approach for direct analysis of QuPPe extracts, low limits of quantification (typically < 5
ng/g) , and associated repeatability (typically < 20%) have been achieved for chlorate,
perchlorate, glufosinate, N-acetyl glufosinate, 3-MPPA, glyphosate, AMPA, Fosetyl-Al,
phosphonic acid, ethephon and more, in a single analysis. Calibration lines were
generated for each analyte. Further details on separation, quantification and validation in
various matrices will be presented.
Food Safety 2017 MCF Spring Symposium
Abstract #20
EXTRACTION AND ANALYSIS OF ORGANOCHLORINE PESTICIDE
RESIDUES IN FATTY MATRIX BY ENHANCED MATRIX REMOVAL-LIPID
AND GC/MSMS
JOAN STEVENS
Agilent Technologies
Most persistent organic pollutants (POPs) are organochlorine pesticides (OCPs) and have
been banned in many countries like North America, Europe and many countries in South
America, in accordance with Stockholm Convention in 1980s. Contamination routes can
lead to bioaccumulation of persistent pesticides in food products of animal origin such as
meats, fish, eggs, milk and processed food that incorporates these ingredients (animal
chows). These high fat food products are considered to be very complex matrix because
of the high fat content and hydrophobic nature of the OCPs. Eliminating matrix
interferences is essential to be able to efficiently analyze OCPs in screening of
contaminated food products. Analysis of complex matrix often requires extensive and
labor intense sample preparation (GPC and SPE) to extract OCPs of interest at the
appropriate concentration, by removing unwanted lipid matrix co-extractives. We
demonstrate the benefits of using Enhanced Matrix Removal-Lipid as a novel dispersive
cleanup material that dramatically reduces matrix co-extractives while maintaining
excellent analytical accuracy and precision without the need for complex sample
preparation techniques. The ease of use, time and cost savings, minimal method
development, and dramatically cleaner extracts make the EMR-Lipid sample cleanup
approach an attractive option for laboratories conducting chemical contamination
analysis, especially from complex fatty matrices.
LC Innovation 2017 MCF Spring Symposium
LC innovation Sessions:
Abstract #7
IMPROVE HPLC SEPARATIONS
BY CAREFULLY MATCHING COLUMN PORE-SIZE TO SOLUTE-SIZE
RICHARD A. HENRY
Independent Consultant
2777 West Gulf Drive, Sanibel, FL 33957
HPLC columns require small, porous particles inside to create adequate surface area and
stationary phase for retention and separation of analytes. Fully-porous or superficially-
porous silica particles have become very popular in HPLC column methods, especially in
reversed-phase (RP) mode. As pharmaceutical interest moves toward larger molecules, it
is important to understand how pore-size and geometry affects column performance in
RP mode for molecules that become too large for rapid diffusion within pore space.
Small molecules with <10Å in their largest dimension have nearly complete access to the
mesopores and stationary phase of any silica particle with an average pore diameter of ca.
80Å or larger. As solutes increase in size, however, restricted movement occurs within
pores to degrade separation performance. Higher MW compounds require selection of
larger-pore columns in the range of 150-1000Å) for a return to optimized performance.
Evidence points to a need for pores in RP columns that are at least 10 times larger than
solutes for rapid diffusion and optimum performance.
Accurate knowledge of column pore-geometry and better information about analyte size
under mobile phase conditions are needed to quickly select the right columns that
minimize trial and error experiments. Performing size exclusion chromatography (SEC)
can become a routine part of HPLC method development because it provides valuable
information about molecular size and accessibility to pores in HPLC column particles.
Accuracy will be improved if SEC and RP columns employ similar pore structures and
mobile phase composition. While examples will focus on aqueous SEC and reversed-
phase (RP) columns, the principles described should be applicable to any HPLC retention
mechanism (HILIC, ion-exchange, etc.).
LC Innovation 2017 MCF Spring Symposium
Abstract #8
IMPACTS OF LIGAND STRUCTURE ON PROTEIN BINDING:
PERFORMANCE OF ION-EXCHANGE MEMBRANES
JERALD K. RASMUSSEN,
CATHY A. BOTHOF, SEMRA COLAK ATAN,
ROBERT FITZSIMONS, GEORGE GRIESGRABER,
FEDERICA SGOLASTRA, ANDREW VAIL
3M Corporate Research Laboratories
3M Center, 201-2N-20, St. Paul, MN 55144
New ligand chemistry designs and membrane modification techniques have allowed us to
develop membrane media with protein binding capacities approaching or exceeding 200
mg/mL of membrane volume. Experimental studies designed to explore the roles of
factors such as ligand density and distribution and graft polymer chain length and
morphology on protein binding performance, indicate that monomer structure has a large
impact on the grafting reaction, which in turn has consequences in terms of ion exchange
properties of the resultant grafted membrane.
The ultimate goal of this research is the design of new materials and devices that provide
an integrated approach to dramatically simplify biopharmaceutical downstream
purification processes through the development of single-use, advanced chromatography
solutions. Some potential applications will be highlighted.
GC Innovation 2017 MCF Spring Symposium
GC innovation Sessions: Abstract #17
QUANTITATIVE CARBON DETECTOR
FOR CALIBRATION-FREE QUANTIFICATION OF COMPLEX MIXTURES
PROFESSOR PAUL J. DAUENHAUER
University of Minnesota
Minneapolis, MN
Quantification of chemical mixtures is the basis for modern chemistry and chemical
process applications related to food, energy, chemicals, pharmaceuticals and agricultural
technologies. Mixtures of organic chemicals can comprise hundreds of compounds,
necessitating expensive and time-consuming separation and detection with conventional
calibration techniques. In this work, we introduce a catalytic microreactor which allows
for calibration-free quantification of organic compounds within gas chromatography.
Analyte compounds eluting from a conventional gas chromatograph column flow into the
microreactor, where a series of catalytic reactions convert each analyte to methane.
Subsequent detection via flame ionization thus results in a common carbon response
factor for all compounds. By this approach, mixtures of hundreds of compounds
including sugars, aldehydes, organic acids, alcohols, thiophenes, and many other
hydrocarbons can be quantified without calibration. The method is introduced with
respect to thermodynamic design constraints, and implementation with conventional gas
chromatograph systems is described.
Short Biography. Professor Paul Dauenhauer serves as the DuPont Young Professor of
Chemical Engineering and Materials Science at the University of Minnesota in
Minneapolis, MN. He received his B.S. in Chemistry and Chemical Engineering from
the University of Wisconsin, Madison, before receiving a Ph.D. in Chemical Engineering
from the University of Minnesota. Following his degree, he was a Senior Research
Engineer at the Dow Chemical Company in Midland, MI, and Freeport, TX. Professor
Dauenhauer’s research on microreactors, fuels, and catalysis addresses frontier research
problems related to sustainability and renewable energy, for which he has received
numerous prestigious awards including the Dept. of Energy – Early Career Award, the
NSF CAREER Award, the Camille Dreyfus Teacher-Scholar Award, the 3M Nontenured
Faculty Award, the Pittcon Achievement Award, and the Rutherford Aris Award for
Excellence in Chemical Reaction Engineering.
GC Innovation 2017 MCF Spring Symposium
Abstract #18
SIMULTANEOUS COMPOUND IDENTIFICATION AND QUANTIFICATION
WITH PARALLEL POLYARC/FID AND MS
CHARLIE SPANJERS
Activated Research Company
Quantification of unknowns with gas chromatography (GC) traditionally requires time-
consuming and costly calibration steps including purchasing, preparing, and analyzing
calibration standards, and applying the calibration results to determine analyte
concentration. In this work, we describe a method for identifying and quantifying
unknowns in a single injection using a parallel Polyarc/FID and mass spectrometer (MS).
Proper configuration of the method requires the use of a pressurized splitter to keep a
constant split ratio as a function of temperature. In this talk, the theory of pressure-driven
flow will be described in relation to the steps that are necessary to keep a constant split
ratio with changing oven temperature. Furthermore, the application of this method to the
analysis of gasoline and blood alcohol will be discussed.