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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.


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.


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.


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.


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.


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.


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.


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.


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


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.


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.


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.


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.

[email protected]

mailto:[email protected]

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.

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