table of contentsstatic1.squarespace.com/static/55432c00e4b067d5d2c8a25d/t... · web viewonline...

ONLINE ABSTRACTS BOOK

23rd Annual Royal Australian Chemical Institute Research and Development Topics Conference in

Analytical and Environmental Chemistry

6th – 9th December 2015

Kolev Research Group,

School of Chemistry,

The University of Melbourne,

Parkville, Melbourne, Victoria, Australia

23rd RACI R&D Topics Conference 6-9 December 2015

Conference Committee

Edward Nagul Lenka O’Connor Šraj

Colin Specht Mandana Ershad

Charles Croft Chelsea Bassett

Special Thanks

Professor Spas Kolev Dr. Inês Almeida

Mrs. Mary Pappa Associate Professor Claire Lenehan

Professor Emily Hilder School of Chemistry – The University of Melbourne

Kolev Research Group

Medallists

Environmental Medallist – Professor David Waite, The University of New South Wales

Peter Alexander Medallist – Dr. David Jeffery, The University of Adelaide

Doreen Clark Medallist – Associate Professor Paul Francis, Deakin University

Best Original Student Paper – Miss Emily Kerr, Deakin University

Judges

A panel of senior researchers from the participating universities headed by Dr. George Khairallah (Accurate Mass Scientific) will judge the oral presentations.

A panel of senior researchers and industry representatives will judge the poster presentations - Awards sponsored by SCIEX.

Megan Gillmore (CSIRO) will judge the Membranes non-chromatographic separation prize.

A panel of senior researchers will judge the Thermo Fisher internship prize.

Past Conference Chairs

Karen Bruce (Flinders University)

Rachel West (Flinders University)

Cover Image

Thanks to Marcus Hammarstedt – UI/UX Designer & Developer

Page | 2


Table of Contents

General Information.................................................................................................................5

Name badges.......................................................................................................................5

Oral Presentations................................................................................................................5

Poster Sessions....................................................................................................................5

Prize Presentation................................................................................................................5

Parking.................................................................................................................................5

Important Numbers...............................................................................................................5

Emergency Evacuation.........................................................................................................5

Campus Map............................................................................................................................6

Activities...................................................................................................................................7

Conference Welcome Mixer - Sunday 6th December...........................................................7

Social Event - Monday 6th December...................................................................................7

Social Event - Tuesday 7th December..................................................................................7

Conference Dinner - Wednesday 9th December...................................................................7

Conference Sponsors..............................................................................................................8

CUSTOM SPONSORS.........................................................................................................8

PLATINUM SPONSORS......................................................................................................8

GOLD SPONSORS..............................................................................................................9

SILVER SPONSORS...........................................................................................................9

BRONZE SPONSORS.........................................................................................................9

IN KIND SPONSORS...........................................................................................................9

Programme at a glance..........................................................................................................10

Oral Presentation Programme...............................................................................................11

Poster Presentation Programme............................................................................................20

Poster Abstracts Monday 7th December.................................................................................24

Poster Abstracts Tuesday 8th December................................................................................38

Poster Abstracts Wednesday 9th December..........................................................................54

Oral Abstracts Monday 7th December....................................................................................68

Oral Abstracts Tuesday 8th December...................................................................................82

Oral Abstracts Wednesday 9th December..............................................................................92

Notes....................................................................................................................................105

Page | 3


Page | 4


General InformationName badgesPlease wear the name badges provided at all conference sessions including during lunch sessions and morning/afternoon tea breaks.

Conference organising committee members, should you want assistance, can be identified by a grey t-shirt with the conference logo printed on the back and “organising committee” printed on the front in blue.

Oral PresentationsOral presentations will be held in the Masson lecture theatre in the Chemistry building; map ref. G17. Delegates presenting oral presentations are requested to contact a conference organising committee member during the registration period at the beginning of their assigned day to have their presentations uploaded onto the computer.

Poster SessionsPoster sessions will be held in the ground floor of the chemistry building; map ref. G17. Posters will be set up by organising committee members on the first full conference day (Monday 7th December); delegates presenting posters are requested to hand in their posters during the registration period in the morning of Monday 7th of December.

Poster boards will be labelled with the number corresponding to the abstract number in this book. Authors presenting posters are requested to be in attendance at their poster for the entire duration of their assigned session.

Prize PresentationAll prizes will be presented at the conference dinner on the evening of the 9th of December.

ParkingThe organising committee does not advise driving to the conference due to limited long-duration parking options around the University of Melbourne. However, if you choose to do so, there are numerous limited time paid parking facilities around the Parkville campus or a paid all day parking facility on the corner of Cardigan and Grattan street in Carlton.

Important NumbersUniversity of Melbourne Security 8344 6666 (Emergency) or 1800 24 6066 (Freecall)

Taxi 131 008

Emergency EvacuationIf an emergency evacuation is necessary during the conference proceedings please exit the building and follow instructions given by emergency wardens, security staff or emergency services. At the end of the evacuation you will be advised when it is safe to return to the building.

Page | 5


Campus Map

Page | 6


ActivitiesConference Welcome Mixer - Sunday 6th Decembero Pizza & Drinks (alcoholic & non-alcoholic) Registration Evening

Venue: The University of Melbourne South Lawn – Map Ref. I14

Time: 5.30PM – 8.00PM

Cost: FREE

Social Event - Monday 6th Decembero Bowling at Strike

Venue: Strike Bowling, Level 3, Melbourne Central, 211 La Trobe Street, Melbourne

Time: 6.30PM – 8.30PM

Cost: $18 per person/per game (Public transport to venue will require a valid MYKI transport card)

Details: Dinner & Drinks (alcoholic & non-alcoholic) can be purchased by delegates at the venue.

o Drinks at Wolf’s Lair, Carlton

Venue: Wolf’s Lair, Jimmy Watson’s Lane, Carlton

Time: 6.30PM – 8.30PM

Details: Nibbles & Drinks (alcoholic & non-alcoholic) can be purchased by delegates at the venue.

Social Event - Tuesday 7th Decembero Royal Botanical Gardens Picnic – Dinner & Drinks (alcoholic & non-alcoholic) provided

Venue: Royal Botanical Gardens Melbourne

Time: 4.10PM – 8.30PM

Cost: FREE (a valid MYKI transport card will be required for delegates to travel to venue)

o Moonlight Cinema, Botanical Gardens – Screening “The Intern”

Venue: Royal Botanical Gardens Melbourne

Time: 8.30PM – 10.30PM

Cost: $16.50 (student) or $19.00 (adult) Note: Delegates are responsible for booking their own tickets

BOOKINGS are ESSENTIAL - https://www.moonlight.com .au/melbourne/movie/the-intern-3/

Conference Dinner - Wednesday 9th DecemberVenue: University House – Map Ref. E13

Time: 7.00PM – 11.00PM

Cost: $70 (please bring cash to registration to purchase tickets)Page | 7

23rd RACI R&D Topics Conference 6-9 December 2015Dress: Semi-Formal

Conference Sponsors

A huge thank-you to our 2015 conference sponsors. Without the generous support of the people and companies below R&D Topics 2015 would not have been possible.

CUSTOM SPONSORS

PLATINUM SPONSORS

Page | 8


GOLD SPONSORS

SILVER SPONSORS

BRONZE SPONSORS

IN KIND SPONSORS

Page | 9


Programme at a glance

Day 1 - 6th Dec Day 2 - 7th Dec Day 3 - 8th Dec Day 4 - 9th Dec

8.00AM - 9.00AMRegistrations Open

8.00AM - 9.00AM Registrations Open

8.00AM - 9.00AM Registrations Open

9.00AM - 9.45AM Conference Opening

Professor Margaret Sheil Melbourne University Provost

9.00AM - 9.30AM Doreen Clark Medallist

A/Prof. Paul Francis

9.00AM - 9.30AM Best Original Student Paper

Miss Emily Kerr9.30AM - 9.50AM

10X Genomics Presentation9.30AM - 9.50AM

Agilent Presentation9.45AM - 10.15AM

Environmental Medallist Prof. David Waite 9.50AM - 11.10AM

Oral Session 49.50AM - 11.10AM

Oral Session 6

10.15AM - 11.35AM Oral Session 1

11.10AM - 11.35AM Morning Tea/Trade Display

11.10AM - 11.35AM Morning Tea/Trade Display

11.35AM - 12.00PMMorning Tea/Trade Display

11.35AM - 12.55PM Poster Session 2

11.35AM - 12.55PM Poster Session 3

12.00PM - 1.20PM Oral Session 2

12.55PM - 1.55PM Lunch/Trade Display

12.55PM - 1.55PM Lunch/Trade Display

1.20PM - 2.20PM Lunch/Trade Display 1.55PM - 2.15PM

Waters Scientific Presentation1.55PM - 2.15PM

Thermo Fisher Presentation



2.20PM - 3.40PMPoster Session 1

3.35PM - 3.50PM Afternoon Tea




3.55PM - 4.25PM Peter Alexander Medallist

Dr. David Jeffery

4.10PM – 8.30PMRoyal Botanical Gardens Picnic

Sponsored By 10X Genomics

4.25PM - 4.45PM PerkinElmer Presentation

4.45PM - 6.05PM Oral Session 35.30PM - 8PM

Conference Welcome Mixer

5.10PM - 5.30PM Conference Closing

7.00PM - 11.00PM Conference Dinner

Sponsored by Elsevier

Page | 10


Oral Presentation Programme

Monday 7 th December

9.00AM CONFERENCE OPENING

Professor Margaret Sheil

Provost, The University of Melbourne

9.45AM Environmental Medallist

Professor David Waite

The University of New South Wales

Oral Session 1 - Chair: Associate Professor Ian McKelvie

10.15AM Charles Croft

The University of Melbourne

EXTRACTION AND SEPARATION OF LANTHANIDES USING POLYMER INCLUSION MEMBRANES

10.35AM Fotouh Mansour

The University of Tasmania

A NEW INNOVATIVE SPECTROPHOTOMETRIC METHOD FOR DETERMINATION OF CONCENTRATION RATIOS IN BINARY MIXTURES

10.55AM Kim Quayle

Deakin University

ELEMENTAL AND MOLECULAR PROFILING OF LICIT, ILLICIT AND NICHE TABACCO

11.15AM Joel Smith

La Trobe University

INVESTIGATING OXAZOLIDINE ADDUCT FORMATION FROM PSEUDOEPHEDRINE

___________________________

11.35AM Morning Tea and Trade Display

___________________________

Page | 11


Oral Session 2 – Chair: Lenka O’Connor Šraj

12.00PM Yong Foo Wong

Monash University

ENANTIOSELECTIVE MULTIDIMENTIONAL GAS CHROMATOGRAPHY FOR THE AUTHENTICITY CONTROL OF AUSTRALIAN M. ALTERNIFOLIA: ADULTERATION OR NATURAL VARIABILITY?

12.20PM Nick Lucas

Flinders University

TRANSFORMING GSR EVIDENCE - ASSESSING THE PERSISTENCE AND TRANSFERENCE OF GUNSHOT RESIDUES

12.40PM Lakmini Egodawatta

The University of Wollongong

IMPACTS OF ARSENIC AND ANTIMONY LABILITY FROM RECENTLY AND HISTORICALLY CONTAMINATED SOILS AND ITS EFFECTS ON WATER SPINACH (IPOMOEA AQUATIC)

1.00PM Yan Li


MINIATURISED MEDIUM PRESSURE CAPILLARY LIQUID CHROMATOGRAPHY SYSTEM WITH FLEXIBLE OPEN PLATFORM DESGIN USING OFF-THE-SHELF MICROFLUIDIC COMPONENTS

______________________

1.20PM Lunch and Trade Display

______________________

2.20PM POSTER SESSION 1

_____________________________

3.40PM Afternoon Tea and Trade Display

_____________________________

3.55PM Peter Alexander Medallist

Doctor David Jeffery

The University of Adelaide

Page | 12


4.25PM Perkin Elmer Sponsor Presentation

Oral Session 3 – Chair: Edward Nagul

4.45PM Kara Spilstead

Deakin University

TOWARDS MICROFLUIDIC FLOW CELLS FOR CHEMILUMINESCENCE DETECTION

5.05PM Christopher Tangvisethpat

The University of Sydney

A MULTI-RESIDUE DRIED BLOOD SPOT METHOD FOR DOPING CONTROL USING AN ALTERNATIVE BLOOD COLLECTION PLATFORM

5.25PM Buddhika Dorakumbura

Curtin University

INVESTIGATIONS INTO THE PHYSICAL PROPERTIES OF LATENT FINGERMARKS USING ATOMIC FORCE MICROSCOPY

5.45PM Megan Gilmore

CSIRO

THE TOXICITY OF ALUMINIUM TO MARINE DIATOMS

6.05PM SOCIAL EVENTS

Page | 13


Tuesday 8 th December

9.00AM Doreen Clark Medallist

Associate Professor Paul Francis

Deakin University

9.30AM 10X Genomics Sponsor Presentation

Oral Session 4 – Chair: Professor Spas Kolev

9.50AM Gabriel Enge


AN AUTOMATED CHROMATOGRAPHY PROCEDURE OPTIMIZED FOR STABLE CU ISOTOPE SEPARATION FROM BIOLOGICAL SOURCE MATERIALS

10.10AM Renée Webster

Monash University

APPLICATION OF MULTIDIMENSIONAL GAS CHROMATOGRAPHY TO ASSESS THE EFFECTIVENESS OF RE-ADDITION OF ANTIOXIDANT TO AGED JET FUELS

10.30AM Sidra Waheed


FABRICATION AND EVALUATION OF POLY (DIMETHYLSILOXANE)-DIAMOND ELECTROPHORETIC CHIP

10.50AM Niki Burns

Deakin University

SELECTIVE DETECTION OF SYNTHETIC CANNABINOIDS

___________________________


___________________________

11.35AM POSTER SESSION 2

Page | 14


______________________


______________________

1.55PM Waters Scientific Sponsor Presentation

Oral Session 5 – Chair: Chelsea Bassett

2.15PM Edward Nagul


THE NATURE OF THE SALT ERROR IN THE SN(II)-REDUCED MOLYBDENUM BLUE REACTION FOR DETERMINATION OF DISSOLVED REACTIVE PHOSPHORUS IN SALINE WATERS

2.35PM Mandana Ershad


STABILITY AND SELECTIVITY OF POLYMER INCLUSION MEMBRANES CONTAINING DINONYLNAPHTHALENE SULFONIC ACID

2.55PM Ghulam Hussain

Curtin University

LOW-CONCENTRATION AMMONIA GAS DETECTION ON MINIATURISED ELECTRODES IN ROOM TEMPERATURE IONIC LIQUIDS

3.15PM Morphy Dumlao


SOLID-PHASE MICROEXTRACTION LOW TEMPERATURE PLASMA MASS SPECTROMETRY FOR THE DIRECT AND RAPID ANALYSIS OF CHEMICAL WARFARE SIMULANTS IN COMPLEX MIXTURES

3.35PM Caitlyn Rogers

Flinders University

AN ALTERNATIVE SAMPLE PREPARATION METHOD FOR THE DETECTION OF DRUGS IN HAIR

____________________________


____________________________

4.10PM ROYAL BOTANICAL GARDENS PICNIC

Page | 15


Wednesday 9 th December

9.00AM Best Original Student Paper Medallist

Emily Kerr

Deakin University

9.30AM Agilent Technologies Sponsor Presentation

Oral Session 6 – Chair: Mandana Ershad

9.50AM Karin van der Pal

Curtin University

SPECTROSCOPIC CHARACTERISATION OF AUTOMOTIVE WINDOW TINT FOR FORENSIC PURPOSES

10.10AM Jalal Althakafy

Monash University

ANALYSIS OF SOME PPCPS AND SELECTED ILLICIT DRUGS IN WATER BY USING UHPLC-ORBITRAP MASS SPECTROMETRY

10.30AM Georgina Sauzier

Curtin University

IN SITU STUDIES INTO THE CHARACTERISATION AND DEGRADATION OF BLUE BALLPOINT INKS BY DIFFUSE REFLECTANCE VISIBLE SPECTROSCOPY

10.50AM Na Kong

Deakin University

REAL-TIME ELECTROCHEMICAL MONITORING OF COVALENT BOND FORMATION IN SOLUTION VIA NANOPARTICLE-ELECTRODE COLLISIONS

___________________________


___________________________

11.35AM POSTER SESSION 3

Page | 16


_______________________


_______________________

1.55PM Thermo Fisher Scientific Sponsor Presentation

Oral Session 7 – Chair: Charles Croft

2.15PM Farhan Cecil


3D PRINTED ON-CAPILLARY PHOTOMETRIC DETECTION DEVICES: LOW COST DETECTOR DESIGNS FABRICATED BY FDM PRINTING

2.35PM Darren Koppel


METAL TOXICITY AND BIOAVAILABILITY TO A POLAR MARINE ALGAE

2.55PM Caroline Watson

Flinders University

CREATING AND INTERPRETING HYPERSPECTRAL DATA FOR VEHICLE PAINTS

3.15PM Alfonso Rojas Cardona


MULTIDIMENSIONAL CHROMATOGRAPHY WITH HIGH RESOLUTION DETECTION FOR THE RESOLUTION OF DISSOLVED ORGANIC MATTER (DOM)

_____________________________


_____________________________

Page | 17


Oral Session 8 – Chair: Colin Specht

3.50PM Tristan Kilmartin

Flinders University

NOVEL METHODOLOGIES FOR THE EXTRACTION OF PLANT METABOLITES

4.10PM Muhammad Zenaidee


FORMATION OF PROTEIN "SUPER-ACIDS": EXTENDING COMPLETE PROTEIN SEQUENCE CHARACTERISATION BY TOP DOWN MASS SPECTROMETRY TO PROTEINS WITH MASSES GREATER THAN 10 KDA

4.30PM Mohammad Sharif Khan

Monash University

COUPLED COLUMN SELECTIVITY INTERPRETED USING SOLVATION PARAMETERS

4.50PM Lenka O’Connor Šraj


INNOVATIVE FLOW-ANALYSIS TECHNIQUES FOR THE TRACE DETERMINATION OF AMMONIA NITROGEN IN MARINE WATERS

5.10PM CONFERENCE CLOSING

7.00PM CONFERENCE DINNER

University House, The University of Melbourne

Page | 18


Page | 19


Poster Presentation Programme

Session 1 Monday 7 th December

1Adam Sutton CHARACTERISATION OF NANOPARTICLE

INTERACTIONS WITH CAPILLARY ELECTROPHORESISUniversity of Tasmania

2Christopher Desire THE DEVELOPMENT OF POROUS POLYMERS FROM

EMULSION TEMPLATES FOR SEPARATION SCIENCEUniversity of Tasmania

3Colin Specht SYNTHESIS OF AU NANOPARTICLES ON POLYMER

INCLUSION MEMBRANES FOR ANALYTICAL APPLICATIONSUniversity of Melbourne

4Georgina Sauzier OPTIMISING THE RECOVERY OF SMOKELESS

GUNPOWDER RESIDUES USING EXPERIMENTAL DESIGN AND TV-SPME/GC-MSCurtin University

5Jared Castle THE STABILITY OF SELECTED PSYCHOACTIVE

SUBSTANCES IN SIMULATED POST-MORTEM BLOODFlinders University

6Jessica Learey EMPLOYING EPR FOR LIPID OXIDATION DETECTION

IN PET FOODDeakin University

7Karen Bruce THE EFFECT OF OLIGONUCLEOTIDE ATTACHMENT

STRATEGIES ON GLASS SURFACES FOR THE DETECTION OF HARMFUL ALGAL BLOOM CAUSATIVE SPECIESFlinders University

8Lifen Chen CO-REACTANT ELECTROCHEMILUMINESCENCE OF

A SERIES OF IRIDIUM(III) COMPLEXES WITH TRI-N-PROPYLAMINEDeakin University

9Mohammad Rahbar EXPLORING THE POTENTIAL OF NANOPARTICLES IN

MICROFLUIDIC PAPER-BASED ANALYTICAL DEVICES FOR RAPID PORTABLE ANALYSIS TARGETED AT FOOD AND AGRICULTURE AREASUniversity of Tasmania

10

Rachel Stephen INVESTIGATING THE SPECIATION OF METALS IN MARINE INDUSTRIAL PROCESS WATERSUniversity of Wollongong

1 Sarah Waras ASSESSING PATHWAYS OF PESTICIDE EXPOSURE

Page | 20


1 IN CHILDREN OF PROFESSIONAL PESTICIDE HANDLERSFlinders University

12

Vipul Gupta 3D PRINTED MINIATURISED ANALYTICAL DEVICES (3D MADe)University of Tasmania

13

Yada Nolvachai FROM MOLECULAR STRUCTURES OF IONIC LIQUIDS TO PREDICTED RETENTION OF FATTY ACID METHYL ESTERS IN COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHYMonash University

Session 2 Tuesday 7 th December

14

Alfonso Rojas Cardona SIMPLE, QUANTITATIVE METHOD FOR THE DETERMINATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS USING HIGH PERFORMANCE COUNTER-CURRENT CHROMATOGRAPHY University of Tasmania

15

Christopher Barnes THE ORIGIN OF TWO NON-ROUTE SPECIFIC IMPURITIES IN METHAMPHETAMINE SYNTHESISED VIA THE NAGAI METHOD Flinders University

16

Christopher Tangvisethpat COMPARISON OF LOW VOLUME QUANTIFIABLE

BLOOD SAMPLING KITS University of Sydney

17

Elisenda Fornells Vernet MEMBRANE ASSISTED ON-LINE EVAPORATIVE CONCENTRATION FOR MICROFLUIDICS University of Tasmania

18

Emily Kerr BLUE ELECTROGENERATED CHEMILUMINESCENCE FROM WATER-SOLUBLE IRIDIUM COMPLEXES Deakin University

19

Hoang-Anh Tu INVESTIGATING LIPOXYGENASE ACTIVITY ON TRILINOLEIN WITHOUT HYDROLYSIS USING INEXPENSIVE SOYBEAN FLOUR Deakin University

20

Lawrence Webb DRYLAB® OPTIMISED TWO-DIMENSIONAL HIGH PERFORMANCE LIQUID CHROMATOGRAPHY FOR DIFFERENTIATION OF EPHEDRINE AND PSEUDOEPHEDRINE BASED METHAMPHETAMINE SAMPLES

Deakin University

21

Luke Andrighetto NANOPARTICLE ASSISTED LASER DESORPTION IONIZATION IN THE ANALYSIS OF DRUGS Deakin University

2 Rachel West EXPLORING THE POTENTIAL OF NANOPARTICLES IN

Page | 21


2MICROFLUIDIC PAPER-BASED ANALYTICAL DEVICES FOR RAPID PORTABLE ANALYSIS TARGETED AT FOOD AND AGRICULTURE AREAS

Flinders University

23

Renzo Fenati DISCRIMINATION OF SINGLE NUCLEOTIDE POLYMORPHISM USING TOE-HOLD MEDIATED STRAND DISPLACEMENT Flinders University

24

Siti Mokhtar SIMULTANEOUS ANALYSIS OF 127 BASIC DRUGS IN FORENSIC CASES BY LIQUID ORBITRAP MASS SPECTROMETRYCHROMATOGRAPHY HYPHENATED WITH HIGH RESOLUTION Monash University

25

Tim Ditcham ANALYSIS OF ORGANICS WITHIN AUSTRALIAN URANIUM ORE CONCENTRATES FOR SOURCE ATTRIBUTION USING SPME-GC/MS AND ATR-FTIR Flinders University

26

Vikashni Nand DEVELOPMENT OF AN AUTOMATED SPECTROPHOTOMETRIC SYSTEM FOR MONITORING OCEAN PH AND ALKALINITYAustralian National

University

27

Wojciech Grochocki THREE-STEP STACKING OF CATIONIC DRUGS BY FIELD-ENHANCED SAMPLE INJECTION, SWEEPING, AND MICELLE TO SOLVENT STACKING IN CAPILLARY ZONE ELECTROPHORESIS University of Tasmania

Session 3 Wednesday 9 th December

14

Ansara Noori PORTABLE IR-LED BASED ATMOSPHERIC MONITORING: AUTOMATED DATA HANDLING OF LARGE DATA STREAMS University of Tasmania

15

Chelsea Bassett THE USE OF 3,4-HPO LIGANDS IN THE DEVLOPMENT OF A MICROFLUIDIC PAPER-BASED ANALYTICAL DEVICE (µ-PAD) FOR THE DETERMINATION OF IRON IN NATURAL WATERS University of Melbourne

16

Claire Szuster ISOTOPIC ANALYSIS OF GAMMA-HYDROXYBUTYRIC ACID (GHB), SYNTHESISED FROM ONE OF ITS PRECURSORS GAMMA-AMINOBUTYRIC ACID (GABA) Flinders University

17

Eliza Moule LAB-ON-A-CHIP MASS SPECTROMETRY TOOLS FOR TESTING ILLICIT DRUGS

Flinders University

18

Holly Yu INVESTIGATIONS INTO THE FATE OF EXPLOSIVES IN SOIL

Curtin University

1 Kelsey Seyfang FORENSIC IDENTIFICATION AND DISCRIMINATION

Page | 22


9 OF GUNSHOT RESIDUE Flinders University

20

Kirsteen Smith USING CHROMATOGRAPHIC TECHNIQUES TO STUDY RETENTION PROCESSES ON POROUS GRAPHITIC CARBON STATIONARY PHASES Deakin University

21

Maddumage Abeywardane VANADIUM PHYTOTOXICITY : VANADIUM AND

NUTRIENT DYNAMICS RMIT University

22

Muhammed Ariful Islam ADVANCED PULSED ELECTROCHEMICAL DTETCTION OPTIONS FOR MICROFLUIDIC AND PAPER FLUIDIC PLATFORMS University of Tasmania

23

Sally Doolette CLASSIFICATION OF ORGANIC MATERIALS WITH LASER INDUCED BREAKDOWN SPECTROSCOPY

Flinders University

24

Simone Madaras THE DEGRADATION OF PSEUDOEPHEDRINE IN SOIL DUE TO MICROBIAL ACTION

Flinders University

25

Yabin Wen PREDICTION OF RETENTION TIMES IN REVERSED-PHASE LIQUID CHROMATOGRAPHY BASED ON CHEMICAL STRUCTURES OF ANALYTES University of Tasmania

26

Mónica Alves

University of Tasmania

APPROACHES TO PORTABLE ANALYSIS OF BIOANALYTES USING MICRO- AND PAPER FLUIDIC PLATFORMS UTILIZING ENZYMATIC ACTIVITIES

Page | 23


Poster AbstractsMonday 7th December

Page | 24


CHARACTERISATION OF NANOPARTICLE INTERACTIONS WITH CAPILLARY

ELECTROPHORESISAdam T. Sutton 1,2, Dario Arrua 1,2, Stuart Thickett 2, Marion Gaborieau 3,4,

Patrice Castignolles 3, Emily F. Hilder 1,2

1 Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Hobart 7001

2 University of Tasmania, School of Physical Sciences, Hobart 7001, 3 ACROSS, Western Sydney University (WSU), School of Science and Health (SSH),

Parramatta, NSW 21504 Molecular Medicine Research Group, WSU, SSH, Parramatta, NSW 2150

[email protected]

Nanoparticles have many applications from pseudo stationary phases in electrokinetic chromatography to drug delivery. When nanoparticles are used in these different systems they are exposed to a number of different molecules. The interactions between the nanoparticles and these molecules vary with the size, shape, hydrophobicity and surface properties of the nanoparticles. Being able to characterise these interactions in complex biological and environmental systems requires a robust and reproducible method [1]. Current methods for characterising these interactions are often tedious and time consuming, thus alternatives are highly desirable [2].

Capillary Electrophoresis (CE) is a fast, inexpensive, robust method capable of examining a variety of nanoparticles. Free solution CE can characterise both the nanoparticles themselves and their interactions with different molecules [3]. However, free solution CE has not been used to examine nanoparticles in complex physiological or environmental areas. Furthermore the reproducibility of free solution CE to examine complex systems is often under scrutiny. Herein we aimed to develop a free solution CE method to study the strength and kinetics of the interaction of proteins and other molecules with nanoparticles in complex physiological or environmental systems. Additionally the reproducibility of free solution CE was assessed using complex oligoacrylate samples to ensure the accuracy of the method.

[1] Malysheva, A.; Lombi, E.; Voelcker, N. H., Bridging the divide between human and environmental nanotoxicology. Nat. Nanotechnol. 2015, 10, 835-844.[2] Mahmoudi, M.; Lynch, I.; Ejtehadi, M. R.; Monopoli, M. P.; Bombelli, F. B.; Laurent, S., Protein-nanoparticle interactions: Opportunities and challenges. Chem. Rev. 2011, 111, 5610-5637.[3] Li, N.; Zeng, S.; He, L.; Zhong, W., Probing nanoparticle-protein interaction by capillary electrophoresis. Anal. Chem. 2010, 82, 7460-7466.

Page | 25


THE DEVELOPMENT OF POROUS POLYMERS FROM EMULSION TEMPLATES FOR SEPARATION SCIENCE

Christopher T. Desire 1, Aminreza Khodabandeh 1, R. Dario Arrua1, Emily F. Hilder1

1 Australian Centre for Research on Separation Science (ACROSS), School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, 7001, Tasmania, Australia

[email protected]

Emulsion templating has emerged as an attractive alternative for the preparation of porous polymers, in particular the polymerisation of high internal phase emulsions (HIPEs) [1]. HIPEs are simply emulsions where the internal phase volume exceeds 74 vol%, which results in a very tight packing of the emulsion droplets. When one or more monomeric species are included in the continuous phase, polymerisation of this phase results in the formation of a highly porous material, which is often referred to as a polyHIPE [1]. PolyHIPEs exhibit a bimodal structure consisting of voids, which are directly templated from the emulsion droplets, and windows, which form between the voids due to the dense packing of the emulsion droplets. It is the windows that provide the material with interconnectivity. Given the role the emulsion has in controlling the morphology, polyHIPEs are considered to be highly tuneable. Changes in the emulsion formulation can result in dramatic changes in structure as well as minor changes, which can allow for fine-tuning. These materials have found applications in areas such as scaffolds for tissue engineering, combinatorial chemistry, catalytic supports and as controlled release devices [1]. Their application in separation science, however, has so far been limited.

In this work we present the development of hydrophobic based polyHIPEs from water-in-oil emulsions. These have been prepared in capillary format with an intended application in both capillary liquid chromatography and capillary electrochromatography (CEC). We have focused on the influence of the emulsion formulation, including the role that emulsification energy plays in determining the porous structure. We have also investigated the possibility to functionalise these hydrophobic scaffolds with water-soluble monomers, which are included in the internal water phase.

References

[1] Kimmins, S. D.; Cameron, N. R. Functional Porous Polymers by Emulsion Templating: Recent Advances. Adv. Funct. Mater. 2011, 21, 211-225.

Page | 26


SYNTHESIS OF Au NANOPARTICLES WITH CONTROLLED SIZE ON THE SURFACE OF

POLYMER INCLUSION MEMBRANES Colin Specht 1, Spas D. Kolev 1, Robert W. Cattrall 1, Tony Spassov2

1 University of Melbourne School of Chemistry, 3010, VIC, Australia2 Sofia University Faculty of Chemistry and Pharmacy, 1164 Sofia, 1 James Bourchier

Blvd., Bulgaria

[email protected]

Research on the use of Polymer Inclusion Membranes (PIMs) for selective extraction of cations or anions is increasing significantly as these represent an attractive alternative to traditional solvent extraction techniques [1]. These membranes consist of a base polymer, a carrier, and in some cases a modifier or plasticizer. A number of stable PIM compositions have been successfully applied to extraction of metal ions, such as Au(III). Metal nanoparticles (NPs) are also an expanding field of study, with a wide range of applications from targeted cancer treatment to catalysis [2]. While extensive metal NP synthesis work has been done, the majority of it has been solution based and interfacing with a stable support remains a challenge for practical applications. Use of a PIM as support by initial extraction of the metal cation followed by a reduction step in aqueous medium was initially done by Kumar et al. [3] and explored further by Bonggotgetsakul et al. [4]. In their work gold nanoparticles were selectively synthesized on either the interior or surface of CTA and PVC based PIMs, respectively. However, significant issues with control of size, stability and distribution of the Au NPs remained.

In this work the synthesis of Au NPs on PIMs has been further explored using a variety of conditions and compositions. PIM compositions consisted of PVC or poly(vinylidene fluoride hexafluoropropylene) (PVDF-HFP) as base polymers and Aliquat-336 or Cyphos IL-101 as carriers. Reducing agents used included EDTA, NaBH4, sodium citrate and oxalic acid. Primary characterization of PIM samples was performed using SEM, AFM and XRD. Supplementary TGA and FT-IR data were obtained for evaluating membrane stability. One of the aims of this work was to enable improved control over Au NPs synthesis for eventual applications in chemical sensing [5] and elucidation of the structure of PIMs.

[1] Almeida, M. I.; Cattrall, R. W.; Kolev, S. D. Recent Trends in Extraction and Transport of Metal Ions using Polymer Inclusion Membranes (PIMs). Journal of Membrane Science.2012, 415, 9-23.

[2] Sardar, R.; Funston, A. M.; Mulvaney, P.; Murray, R. W. Gold Nanoparticles: Past, Present, and Future. Langmuir.2009, 25, 13840-13851.

[3] Pandey, K. R.; Tyagi, A. K.; Dey, G. K.; Ramagiri, S. V.; Bellare, J. R.; Goswami, A. In Situ Formation of Stable Gold Nanoparticles in Polymer Inclusion Membranes. Journal of Colloid and Interface Science.2009, 337, 523-530.

[4] Bonggotgetsakul, Y. N.; Cattrall, R. W., Kolev, S. D. The Preparation of a Gold Nanoparticle Monolayer on the Surface of a Polymer Inclusion Membrane using EDTA ad the Reducing Agent. Journal of Membrane Science.2011, 379, 322-329.

[5] Saha, K.; Agasti, S. S.; Kim, C.; Li, X.; Rotello, V. M. Gold Nanoparticles in Chemical and Biological Sensing. Chemical Reviews.2012, 112, 2739-2779.

Page | 27


OPTIMISING THE RECOVERY OF SMOKELESS GUNPOWDER RESIDUES USING EXPERIMENTAL

DESIGN AND TV-SPME/GC-MSGeorgina Sauzier 1,2, Dana Bors 3, Jordan Ash 3, John V. Goodpaster 3 and

Simon W. Lewis 1,2

1 Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845, Australia.

2 Nanochemistry Research Institute, GPO Box U1987, Perth, Western Australia 6845, Australia

3 Department of Chemistry and Chemical Biology, Indiana University-Purdue University, Indianapolis, IN 46202

[email protected]

In recent decades, the use of explosives and explosive devices has become an increasing topic of public concern. Successful investigation of such events is heavily reliant upon the recovery of residues from the scene, their preservation during storage or transportation, and their subsequent extraction for analysis. However, these objectives may be affected by several inter-related factors such as the sampling method, storage conditions, and time between collection and analysis.

This study employed a central composite design (CCD) to determine optimal protocols for the sampling, storage and extraction of explosive residues originating from smokeless gunpowder. Analysis was carried out using total vaporisation solid phase microextraction gas chromatography-mass spectrometry (TV-SPME/GC-MS) [1], which was able to successfully detect three main components present in smokeless gunpowder at trace (< 1 ppm) concentrations. It was found that optimal recovery of these components was obtained using isopropanol-wetted cotton swabs stored under refrigerated conditions, analysed on the same day as residue collection with a 15 minute extraction into acetone. These optimised protocols were then applied to the recovery of post-blast residues deposited on steel witness plates following the detonation of a PVC pipe bomb device. Higher levels of explosive were recovered from plates facing the sides of the device; consistent with failure of the device initiating in the pipe body. It is anticipated that the methods employed in this study may be applicable to a variety of other explosive compounds, and thus assist in establishing a set of ‘best practice’ procedures for the successful investigation of explosive incidents.

References:

[1] Rainey, C.L.; Bors, D.E.; Goodpaster, J.V. Design and optimization of a total vaporization technique coupled to solid phase microextraction (TV-SPME). Analytical Chemistry. 2014, 86 (22), 11319-11325.

Page | 28


THE STABILITY OF SELECTED PSYCHOACTIVE SUBSTANCES IN SIMULATED POST-MORTEM

BLOODJared W. Castle 1, K. Paul Kirkbride1, G. Stewart Walker1, Claire E.

Lenehan1, Danielle M. Butzbach2, Frank Reith3, Sam Costello4

1 School of Chemical and Physical Sciences, Flinders University, Bedford Park, 5042, SA, Australia

2 21 Divett Place, Forensic Science SA, Adelaide, 5000, SA, Australia3 School of Biological Sciences, The University of Adelaide, Urrbrae, 5064, SA, Australia

4 Department of Gastroenterology, The Queen Elizabeth Hospital, Woodville South, 5011, SA, Australia

[email protected]

In autopsy cases, forensic toxicologists are often required to identify drugs, their known degradation products, and metabolites in the body. After death, microorganisms present in the gastrointestinal tract can translocate into body tissues and blood. These microorganisms, as well as external invaders, may degrade drugs and metabolites, both before and after specimen collection at autopsy, thus complicating the analyses. There are few studies regarding the pathways by which drugs may degraded post mortem, however it has been reported that in some cases, a drug or metabolite may be entirely converted into another compound and not detected at all, resulting in important evidence concerning the cause or manner of death potentially being overlooked [1-2]. Therefore, knowledge of drug stability in post-mortem specimens is essential for interpreting post-mortem toxicology results.

This research examines the stability of selected psychoactive drugs in simulated post-mortem blood. The simulated blood is constructed from ante-mortem blood inoculated with human faeces, approximating the microbial community expected in real post-mortem blood due to microbial translocation from the gastrointestinal tract into the bloodstream after death. The effect of temperature and preservatives on the stability of the psychoactive drugs will be examined, and degradation products identified, using a combination of liquid chromatography-UV detection, gas chromatography-mass spectrometry, and liquid chromatography quadrupole time-of-flight mass spectrometry.

This research will inform forensic toxicologists as to whether the selected psychoactive drugs degrade in the post-mortem interval until analysis and whether additional caution must be exercised in regards to interpreting blood concentrations of these drugs.

[1] Butzbach, D. M.; Stockham, P. C.; Kobus, H. J.; Noel Sims, D.; Byard, R. W.; Lokan, R. J.; Stewart Walker, G., Bacterial Degradation of Risperidone and Paliperidone in Decomposing Blood. J. For. Sci. 2013, 58 (1), 90-100.

[2] Butzbach, D. M.; Stockham, P. C.; Kobus, H. J.; Noel Sims, D.; Byard, R. W.; Lokan, R. J.; Stewart Walker, G., Stability of Serotonin-selective Antidepressants in Sterile and Decomposing Liver Tissue. J. For. Sci. 2013, 58 (S1), S117-S125.

Page | 29


EMPLOYING EPR FOR LIPID OXIDATION DETECTION IN PET FOOD

Jessica J. Learey 1, Jacqui L. Adcock 1, Shona Crawford 2, Colin J. Barrow 1

1 Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences, Deakin University, Waurn Ponds, VIC, Australia

2 Kemin, Building nd, Deakin University, Waurn Ponds, VIC, Australia

[email protected]

Omega-3 and omega-6 fatty acids are added to pet food due to their health benefits, however these ingredients are highly unstable and undergo minor oxidation leading to off-odours and flavours even at very low levels [1]. This study aimed to develop simple and sensitive methods capable of monitoring these lipid oxidation processes through the use of electron paramagnetic resonance (EPR). In this work we demonstrate the potential of EPR for monitoring changes in the concentrations of radical intermediates formed during this degradation process and explore the effects of antioxidants that may be present in pet foods. While further analysis is required in this field, the technique has shown potential advantages over currently employed methods in terms of its simplicity and sensitivity.

Page | 30


THE EFFECT OF OLIGONUCLEOTIDE ATTACHMENT STRATEGIES ON GLASS SURFACES FOR THE

DETECTION OF HARMFUL ALGAL BLOOM CAUSATIVE SPECIES

Karen L. Bruce 1, Amanda E. Ellis 2, Sophie C. Leterme 3 and Claire E. Lenehan 1

1 School of Chemical and Physical Sciences, Flinders University, 5042, SA, Australia2 Flinders Centre for Nanoscale Science and Technology, Flinders University, 5042, SA,

Australia3 School of Biological Sciences, Flinders University, 5042, SA, Australia

[email protected]

Harmful algal bloom (HAB) events have become more prevalent in the last few decades, with each event leading to the potential release of biotoxins in our waterways. Bloom monitoring is essential to prevent detrimental damage to the environment and human health. Traditional methods using light microscopy can encounter difficulties in discriminating between toxic and non-toxic HAB causative species of the same genus due to similarities in cellular morphology. Alternatively, specific, and highly discriminative detection can be achieved using oligonucleotide probes that are able to target variable regions found within the rRNA of HAB species.

Detection using surface immobilized oligonucleotides is advantageous as binding and pre-concentration of the target rRNA sequence from the sample matrix is possible. To remove non-specific attachment of alternate sequences a simple washing method is used making it a highly selective technique. Previously attachment has been achieved using a streptavidin-biotin interaction which provides a strong, non-covalent attachment of the oligonucleotides to the surface. More recently however, a range of covalent strategies have been developed to allow for greater manipulation at the surface including the use of spacers to optimize the distance of the oligonucleotide from the surface, preventing steric hindrance effects. Overall, this method can provide a more robust, and potentially reusable, surface.

Here we demonstrate the attachment of oligonucleotide capture probes to generic glass microscope slides. Two different attachment strategies were employed, a common amine silanization technique as well as a vinyl silanization method. These strategies provide an insight into how the chemistry of the modified surface is able to influence the effectiveness of the final detection device.

This poster will compare the distinctly different surface modification strategies and discuss the advantages and disadvantages of each as a potential detection platform for HAB species Alexandrium catenella.

Page | 31

23rd RACI R&D Topics Conference 6-9 December 2015CO-REACTANT ELECTROCHEMILUMINESCENCE OF A SERIES OF IRIDIUM(III) COMPLEXES WITH

TRI-N-PROPYLAMINELifen Chen 1, Emily Kerr 1, Egan H. Doeven1, Paul S. Francis1

1 Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences, Deakin University,75 Pigdons Road, Waurn Ponds, Victoria 3216, Australia

[email protected]

Electrochemiluminescence (ECL) combines the advantages of electrochemistry and chemiluminescence, such as high sensitivity, ease of spatial and temporal control, and applicability to a wide range of analytical techniques [1]. It has become an important and valuable analytical technique. Among ECL systems, the co-reactant ECL based on tris(2,2’-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) and tri-n-propylamine (TPrA) has been explored and used in many areas. In the recent decade, iridium(III) complexes have attracted great interest as alternative ECL reagents due to their favourable electrochemical properties [2]. In contrast to ruthenium complexes, they possess long lifetimes and high photoluminescence efficiencies, and most importantly, their emission maxima can be tuned from near-infrared to deep-blue-visible light by incorporating different functional groups on their ligands.

Since the initial iridium-based co-reactant ECL involving tris(2-phenylpyridine)iridium(III) (Ir(ppy)3) was observed by Bruce and co-workers [3], many heteroleptic iridium(III) complexes have been studied as ECL luminophores. However, few iridium(III) luminophores have be used for real-world applications. In order to better understand the fundamental electron transfer and light emission properties, the co-reactant ECL intensity of a series of iridium complexes has been explored. A combination of spectroscopic, electrochemical and photographic techniques has provided a comprehensive comparison of the ECL properties of the complexes. This study has revealed that the previous preliminary reports by other research groups of exceptionally high co-reactant ECL intensities from iridium(III) complexes with TPrA may be overstated.

[1] Doeven, E.H.; Barbante, G. J.; Kerr, F; Hogan, C. H.; Endler, J. A.; Francis, P. S. Red–Green–Blue Electrogenerated Chemiluminescence Utilizing a Digital Camera as Detector . Anal. Chem.2014, 86, 2727-2732.

[2]Kerr, E; Doeven, E. H.; Barbante, G. J.; Hogan, C. F.; Bower, D. J.; Donnelly P. S.; Connell, T. U.; Francis, P.S. Annihilation electrogenerated chemiluminescence of mixed metal chelates in solution: modulating emission colour by manipulating the energetics. Chem. Sci. 2015, 6,472-479.

[3] Bruce, D.; Richter,M. M.; Green electrochemiluminescence from ortho-metalated tris(2-phenylpyridine)iridium(III), Anal. Chem. 2000, 74, 1340-1342.

Page | 32

23rd RACI R&D Topics Conference 6-9 December 2015EXPLORING THE POTENTIAL OF NANOPARTICLES IN MICROFLUIDIC PAPER-BASED ANALYTICAL DEVICES

FOR RAPID PORTABLE ANALYSIS TARGETED AT FOOD AND AGRICULTURE AREAS

Mohammad Rahbar1, Pavel Nesterenko1, Brett Paull1, Mirek Macka 1

1School of Physical Sciences and Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75, Hobart 7001, Australia

[email protected]

The demand for portable food analysis has been increasing following requirements to ensure food safety and quality. Therefore the focus of analytical scientists is increasingly design of portable analytical devices that would allow fast, low-cost, and robust on-site detection of biological and chemical contaminants in food. Up to now, different analytical methods have been used in food analysis but the majority of them are not portable, while those portable ones suffer severe limitations [1].

Microfluidic systems have been explored for on-site analysis and among them paper-based microfluidic analytical devices (μPADs) have been gaining attention due to their unique advantages. Paper-based microfluidics is a low-cost, portable, easy-to-use, and equipment-free alternative to other analytical techniques. Fabrication of μPADs involves several steps, with a key step in creating hydrophilic-hydrophobic capillary channels on a sheet of paper, often by creating (printing) hydrophobic brakes as lines where the typically aqueous sample and reagents cannot penetrate [2]. However, μPADs also have limitations, which include sometimes limited sensitivity and accuracy. Improved selectivity and sensitivity could be achieved by employing some nanomaterials, such as nanoparticles, which have physical dimensions orders of magnitude below the dimensions of pores in μPADs. Quantum dots (QDs), metal nanoparticles and nanocomposites have some extraordinary physical and chemical characteristics, which can be utilised in various analytical platforms. In this project we will explore the use of these materials to design more selective, specific and sensitive μPADs applicable in portable, multiplex and rapid analysis of food and agricultural analysis.

[1] Ricci, F.; Volpe, G.; Micheli, L.; Palleschi, G., A review on novel developments and applications of immunosensors in food analysis. Analytica Chimica Acta 2007, 605 (2), 111-129.

[2] Cate, D. M.; Adkins, J. A.; Mettakoonpitak, J.; Henry, C. S., Recent developments in paper-based microfluidic devices. Analytical Chemistry 2015, 87 (1), 19-41.

Page | 33


INVESTIGATING THE SPECIATION OF METALS IN MARINE INDUSTRIAL PROCESS WATERS

Rachel N. Stephen 1, Dianne F. Jolley 1

1 University of Wollongong, Northfields Ave Wollongong, 2522, NSW, Australia

[email protected]

To understand and manage the risk posed by metals to aquatic marine life, it is important to determine the influence of water chemistry parameters on the speciation and lability of metals in industrial effluents. To investigate the physical speciation of eight metals (Cr, Fe, Cu, Zn, Cd, Pb, As and Se), measurements of total and dissolved metal concentrations were made over a two month period at five sites, including a clean coastal reference site and four sites within an industrial area, which utilizes seawater for cooling processes. The chemical equilibrium model, Windermere Humic Aqueous Model (WHAM) VII was employed to determine the lability of some metals (Cu, Zn, Cd and Pb) in these waters. Maximum dynamic metals concentrations, determined from dissolved metal concentrations and WHAM predictions, were compared with labile metal concentrations measured by the passive sampling technique, diffusive gradients in thins films (DGT), to investigate the bioavailability of metals at the industrial sites.

Concentrations of total and dissolved metals were below Australian water quality guidelines for the protection of 90 and 95% of marine organisms, respectively, with the exception of one industrial site. Comparisons between DGT-labile concentrations and maximum dynamic concentrations indicated poor agreement for all metals studied. The most plausible reason for the deviation was that DGT devices were exposed to irregular inputs of metals throughout the deployment period, combined with the fact that maximum dynamic concentrations were calculated from a single grab sample measurement, rather than from a mean of multiple grab samples. Nevertheless, these comparisons were still informative providing interpretations of potential bioavailability at the time of sampling. Overall, dissolved Cd, Zn and Pb were identified to be more bioavailable than Cu, due to their higher proportion of inorganic species predicted by WHAM.

Page | 34


ASSESSING PATHWAYS OF PESTICIDE EXPOSURE IN CHILDREN OF PROFESSIONAL PESTICIDE

HANDLERMaisarah N. Waras 1, Claire Lenehan 2, Kateryna Babina1

, John Edwards1

1 School of the Environment, Faculty of Science and Engineering, Flinders University2 School of Chemical and Physical Science, Faculty of Science and Engineering, Flinders

University

[email protected]

Pesticides comprise a wide range of substances that are used to prevent, destroy, repel or mitigate pests. Unfortunately, they are not always selective for their intended target organisms. Inadvertent exposure of pesticides may occur and it can result in adverse health effects in humans. Pesticides exposure is often studied in the pesticide handler (the workers) but it is also suggested that workers may bring the chemicals that they are exposed with to the family member. Children are the particularly vulnerable to the effects of pesticide exposure. Low level exposure to pesticide in childhood has been linked to poorer health outcomes, neurodevelopmental deficits, childhood leukaemia and other cancers. The aim of this study is to identify intervention strategies (at the workplace or at home) in order to reduce the exposure to pesticides amongst Australian children. This will be achieved by 1) identifying the exposure pathways (take-home pathway) and 2) the extent of pesticide exposure of the children of pesticides handler. This research will involve a group of selected pesticides which are chlorpyrifos, deltamethrin, piperonyl butoxide, glyphosate, oxyfluorfen, trifluralin, cypermethrin, MCPA, 2-4-D, simazine and chlortholanil. The participants will be selected based on any households in South Australia comprising at least a child of 2-6 years old and two adults, one of whom is an occupational pesticides handler. Analyses of the selected pesticides in house and vehicle dust and wipe sample obtained from the participants’ house and vehicles will assist to identify the pathway of exposure. While the analyses of urine sample collected from both parents and the children will give information of the extent of pesticide exposure. These analyses will be done in GC/MS. The outcome of the study is expected to identify the potential intervention strategies to minimise the risks to Australian children’s health from pesticide exposure.

Page | 35


3D PRINTED MINIATURISED ANALYTICAL DEVICES

(3D MADe)Vipul Gupta1,2, Pavel Nesterenko1, Brett Paull1,2

1 Australian Centre for Research on Separation Sciences (ACROSS), School of Physical Sciences, University of Tasmania, Sandy Bay, Hobart 7001, Tasmania, Australia.

2ARC Centre of Excellence for Electromaterials Science, School of Physical Sciences, University of Tasmania, Sandy Bay, Hobart 7001, Tasmania, Australia.

[email protected]

In just three decades of its genesis, 3D Printing is revolutionising every field of science and technology and analytical sciences is no exception. Here the use of 3D printing technology to produce chromatographic column hardware, and high pressure resistive electro-osmotic micro pumps is described.

The chromatographic column hardware comprising of 600 mm long, 0.9 mm i.d. double handed spiral channel enclosed within a 5 × 30 × 30 mm footprint was produced through selective laser sintering (SLS) in stainless steel and titanium alloy (Ti-6Al-4V). The production in stainless steel and titanium alloy allowed their use for generation of octyl decyl silica (ODS) particle packed bed and poly(butyl methacrylate-co-ethyleneglycoldimethacrylate) (BuMA-co-EDMA) monolith, respectively. These columns were applied to the reversed-phase liquid chromatographic separation of small (homologous phenones) and large molecules (proteins and peptides). The latter provided the high resolution separation of 10 proteins including A and B components of β-lactoglobulin by circumventing current surface roughness limitations of SLS.

High pressure resistive electro-osmotic micro pump was generated using photonic crystal fibres and 3D polyjet printed platforms. A Photonic crystal fibre with 125 parallel 4 µm i.d. channels was used to provide high charge/volume ratio to overcome the inability of electro-osmotic pumps in generating flow against high back-pressure. These fibres were further housed within 3D printed platforms to provide them better strength, ease of serial or parallel arrangements and allowing a plug and play operation. They were characterised and compared with conventional fused silica capillaries for electro-osmotic flow rate, maximum resistive back-pressure, and joule heating at field strengths ranging from 250 V/cm to 600 V/cm. The fibre used herein provided more than 100 fold increase in maximum resistive back-pressure while still maintaining the similar volumetric flow rate and generating less joule heating as compared to a fused silica capillary of equivalent area of cross-section.

Page | 36


FROM MOLECULAR STRUCTURES OF IONIC LIQUIDS TO PREDICTED RETENTION OF FATTY

ACID METHYL ESTERS IN COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY

Yada Nolvachai, Chadin Kulsing, Annie Xu Zeng, Sung-Tong Chin, Blagoj Mitrevski, Philip J. Marriott

Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Wellington Road, Clayton, VIC 3800, Australia

[email protected]

Ionic liquids (IL) are attractive stationary phases to broaden selectivity in gas chromatography (GC). The rational design, selection and application of IL in comprehensive two-dimensional GC is a desirable goal. In this study, methods to predict two dimensional chromatograms of fatty acid methyl esters (FAME) starting from given structures of IL stationary phases and their interactions with FAME solutes are described. Molecular parameters of dipole moment, lowest unoccupied molecular orbital energy and molar volume of different ionic liquids were calculated by using GAUSSIAN. With established correlations between molecular simulation and linear solvation energy relationships, molecular parameters were converted to s, e and l values for stationary phase descriptors. This allows reliable prediction of equivalent chain length of FAME on each ionic liquid column. Isovolatility curves in GC×GC space of reference saturated FAME were then determined for each IL column in order to take into account the dependence of retention time on temperature in temperature programmed separation. The resulting predicted GC×GC chromatograms were compared with previously reported experimental results with good correlation. [1]

[1] Kulsing, C.; Nolvachai, Y.; Zeng, A.X.; Chin, S.-T.; Mitrevski, B.; Marriott, P.J. From molecular structures of ionic liquids to predicted retention of fatty acid methyl esters in comprehensive two-dimensional gas chromatography. ChemPlusChem 2015, 79, 790-797.

Page | 37


Poster AbstractsTuesday 8th December

Page | 38


SIMPLE, QUANTITATIVE METHOD FOR THE DETERMINATION OF DISSOLVED ORGANIC MATTER IN NATURAL WATERS USING HIGH

PERFORMANCE COUNTER-CURRENT CHROMATOGRAPHY

Alfonso Rojas, a Sara Sandron,a Richard Wilson,b Noel W. Davies,b Paul R. Haddad,a Robert A. Shellie,a Pavel N. Nesterenko,a and Brett Paulla*

a Australian Centre for Research on Separation Sciences (ACROSS), School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania, Australia 7001, email: [email protected]; Fax: +61 (03) 6226 2858; Tel: +61 (03) 6226 6680.

b Central Science Laboratory (CSL), University of Tasmania, Private Bag 74, Hobart, Tasmania, Australia 7001.

alfonso,rojascardona @utas.edu.au

A simple, high-performance counter-current chromatography method with sequential UV absorbance (254 nm) and evaporative light scattering detection (ELSD) was developed for the quantification of dissolved organic matter (DOM) extracted from natural waters. The method requires extraction of only small volumes of water sample carried out using solid-phase extraction (SPE) on poly(styrenedivinylbenzene)-based extraction cartridges (Varian PPL). The concentrated DOM was quantified using reversed-phase high-performance counter-current chromatography (HPCCC), with a water/methanol (5:5) mobile phase and hexane/ethyl acetate (3:7) stationary phase. The critical chromatographic parameters were optimised, applying a revolution speed of 1900 rpm and a flow-rate of 1 mL min-1. Under these conditions, 50 μL of extracted DOM solution could be injected and quantified using calibration against a reference natural dissolved material (Suwannee River), based upon UV absorbance at 254 nm and ELSD detection. Both detection methods provided excellent linearity (R2>0.995) for DOM across the concentration ranges of interest, with limits of detection of 4 µg ml-1 and 7 µg ml-1 for ELSD and UV absorbance, respectively. The method was validated for peak area precision (<5%), and accuracy and recovery based upon spiking seawater samples prior to extraction, together with DOM solutions post-extraction (>95% recovery). The developed method was applied to the determination of the concentration of DOM in seawater, based upon initial sample volumes as small as 20 mL.

Page | 39


THE ORIGIN OF TWO NON-ROUTE SPECIFIC IMPURITIES IN METHAMPHETAMINE SYNTHESISED VIA THE NAGAI

METHODChristopher Barnes1, Martin Johnston1, K. Paul Kirkbride1

1 Flinders University, Bedford Park 5042, SA, Australia

[email protected]

Methamphetamine (MA) is an illicit drug and one of the most widely used drugs in Australia and worldwide [1]. A number of impurities arise in MA as a result of side reactions which occur during synthesis. The exact impurities found vary based on a number of factors including the synthetic route used and reaction conditions employed [2]. Forensic investigators are therefore able to look at impurities in seized MA to provide forensic intelligence as to the synthetic methods used by clandestine laboratories, and to link seizures.

N-formylmethamphetamine (FMA) is an impurity thought to only occur in MA synthesised via the Leuckart method [3], however it has since been found, along with N-acetylmethamphetamine (AMA), in MA synthesised via the Nagai method [4]. This study looks into the origin of these two impurities, as there are no obvious sources of formylation of acetylation in the Nagai reaction.

The results from this study show that AMA is formed from a reaction between MA and phenyl-2-propanone (P2P), a known impurity in MA. The results also indicate that FMA is produced from an unknown formylating agent present in the reaction mixture. Several potential sources of FMA formation have been analysed and shown to either not contribute to FMA formation, or do so at levels significantly lower than what is detected in MA.

References

1. UNODC, World Drug Report. 2014, United Nations: New York.2. Cantrell, T.S., et al., A study of impurities found in methamphetamine synthesized from ephedrine. Forensic Science

International, 1988. 39(1): p. 39-53.3. Sanger, D.G., I.J. Humphreys, and J.R. Joyce, A review of analytical techniques for the comparison and

characterization of illicit drugs. Journal of the Forensic Science Society, 1979. 19(1): p. 65-71.4. Qi, Y., I. Evans, and A. McCluskey, New impurity profiles of recent Australian imported 'ice': Methamphetamine

impurity profiling and the identification of (pseudo)ephedrine and Leuckart specific marker compounds. Forensic Science International, 2007. 169(2-3): p. 173-180.

Page | 40


COMPARISON OF LOW VOLUME QUANTIFIABLE BLOOD SAMPLING KITS

Christopher Tangvisethpat 1,2, Janelle Grainger 1, Catrin Goebel 1, Adrian V. George 2

1 Australian Sports Drug Testing Laboratory, National Measurement Institute, 105 Delhi Road, North Ryde 2113, NSW, Australia

2 School of Chemistry, The University of Sydney 2006, NSW, Australia

[email protected]

Dried blood spots (DBS) are a desirable matrix for anti-doping due to their small sampling volume, minimally invasive sampling, tamper resistance, and ease of transportation and storage [1]. Traditional DBS filter paper media results in inconsistent sampling volumes, dependent on blood sample viscosity [2]. Three commercially available alternative blood collection platforms were compared in this study, using over 200 analytes across 8 prohibited substance classes, to assess their suitability for superseding traditional DBS media in doping control. These products were the Shimadzu Noviplex™ cards, Phenomenex Mitra™ microsamplers and Tomtec DBS slides. Performance was assessed by the intensity of background interferences resulting from the manufacturing of each platform, and by sensitivity of the products for detecting analytes. The Noviplex™ cards, sampling the smallest volume, have intense inherent interferences. The Mitra™ and Tomtec products showed generally equivalent performance, with the Tomtec DBS platform showing slightly greater sensitivity for low concentration analytes, attributed to their higher sampling volume. All sampling products also demonstrated dilution factors as a result of differences between the initial sampling volume and reconstitution for instrumental analysis. Relatively larger platform sampling volumes and low background favoured sensitivity for the Mitra™ and Tomtec platforms. However, general insensitivity due to inherently low dried blood spot sample volumes highlighted the need for more sensitive instrumentation to compensate for this.

References:

[1] Sharma, A.; Jaiswal, S.; Shukla, M.; Lal, J., Dried blood spots: Concepts, present status, and future perspectives in bioanalysis. Drug Test. Anal. 2014, 6 (5), 399-414.

[2] O'Mara, M.; Hudson-Curtis, B.; Olson, K.; Yueh, Y.; Dunn, J.; Spooner, N., The effect of hematocrit and punch location on assay bias during quantitative bioanalysis of dried blood spot samples. Bioanalysis 2011, 3 (20), 2335-2347.

Page | 41


MEMBRANE ASSISTED ON-LINE EVAPORATIVE CONCENTRATION FOR MICROFLUIDICS

Elisenda Fornells1,2,3, Michael Breadmore1,3, Emily Hilder1,3, Robert Shellie2,3, Mike Bailey2,3

1ASTech, University of Tasmania, 7000, Hobart TAS, Australia2ASTech, Trajan Scientific and Medical, 3134, Ringwood VIC, Australia

3ACROSS, University of Tasmania, 7005, Sandy Bay TAS, Australia

[email protected]

The incorporation of concentration stages in micro-scale analytics is becoming a necessary tool in the development of new analysis procedures, as their small dimensions can hinder their practical applications when handling low-abundance analytes. Multiple principles for sample concentration in microfluidics have been explored and reported in the literature, one of them being solvent removal via evaporation through vapor permeable membranes 1. This technique is advantageous because evaporation of small quantities of fluids can be extremely rapid, while the membrane interface provides a controlled process environment.

However, the described procedures are performed in static conditions keeping the sample in contact with a membrane during a period of time before it is retrieved and analysed. As a consequence they can face long concentration times and unknown concentration factors. Sample loss occurs as well due to residue left in the channels and membranes, which require cleaning after use 1–3. As such, and for other reasons, these procedures do not always lend themselves to viable routine and commercial applications. To avoid some of these issues we present a new approach allowing concentration of an online flow by membrane assisted evaporation. Several designs have been explored and its performance assessed under different operating conditions such as temperature or flow. Results show good relationship between concentration factor achieved and the flow-dependent concentration time.

References:

[1] Sharma, N. R., Lukyanov, A., Bardell, R. L., Seifried, L.; Shen, M. Development of an evaporation-based microfluidic sample concentrator. Microfluid. BioMEMS, Med. Microsystems VI. 2008, 6886, 68860R–9.

[2] Zhang, J. Y.; Do, J.; Premasiri, W. R.; Ziegler, L. D.; Klapperich, C. M. Rapid point-of-care concentration of bacteria in a disposable microfluidic device using meniscus dragging effect. Lab Chip. 2010, 10, 3265–3270.

[3] Tseng, W.-Y.; van Dam, R. M. Compact microfluidic device for rapid concentration of PET tracers. Lab Chip. 2014, 14, 2293–302 (2014).

Page | 42


BLUE ELECTROGENERATED CHEMILUMINESCENCE FROM WATER-SOLUBLE IRIDIUM COMPLEXES

Emily Kerr 1, Egan H. Doeven 2, Gregory J. Barbante 3, Paul S. Francis 1

1 Deakin University, Geelong, Australia. School of Life and Environmental Sciences, Centre for Chemistry and Biotechnology. Locked Bag 20000, Geelong, Victoria 3220, Australia.

2 Deakin University, Geelong, Australia. School of Life and Environmental Sciences, Centre for Regional and Rural Futures. Locked Bag 20000, Geelong, Victoria 3220, Australia.

3 School of Physical Sciences, Chemistry | Faculty of Science, Engineering and Technology; University of Tasmania, Sandy Bay TAS 7005

[email protected]

Electrogenerated Chemiluminescence (ECL) is a powerful analytical tool used in many bioanalytical detection systems.[1] In an ECL-based assay, the biomolecule of interest is ‘labelled’ with a compound capable of emitting light upon application of an electrical trigger. The resulting light can be measured, providing a highly sensitive and accurate measure of that biomolecule in the sample. Only one ECL label has been successfully utilised for commercial bioanalytical applications, an orange-light emitter: tris(2,2′-bipyridyl)ruthenium(II) ([Ru(bpy)3]2+). Previous work by our research group has focussed on the development of iridium complexes that emit blue ECL, and their incorporation into the first multicolour (multiplexed) ECL detection systems (with [Ru(bpy)3]2+), utilising a digital camera for detection.[2,3] However, the low water solubility of these blue emissive complexes has severely limited their subsequent incorporation into bioanalytical ECL applications. To address this shortcoming, a variety of water soluble iridium complexes were developed which incorporated highly polar sulfonated phenylpyridines and tetraethylene glycol (TEG)-derivatized triazolylpyridines to enhance aqueous solubility along with previously developed strategies to impart a blue-shift in the ECL emission.[4] The developed complexes exhibited blue or green ECL emission maxima between 456 and 482 nm and the most intense, blue-shifted emitter [Ir(df-ppy)2(pt-TEG)]+ (df-ppy=2-(2,4-difluorophenyl)pyridine anion, pt-TEG=1-(2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethyl)-4-(2-pyridyl)-1,2,3-triazole) exhibited ECL 102% of [Ru(bpy)3]2+ with tri-n-propylamine as a co-reactant in aqueous phosphate buffer. This demonstration of bright blue ECL from a water soluble iridium complex in analytically useful conditions is a promising step forward in the development of multicolour bioanalytical ECL detection systems.

[1] Richter, M. M. Chemical Reviews 2004, 104, 3003.

[2] Barbante, G. J.; Doeven, E. H.; Kerr, E.; Connell, T. U.; Donnelly, P. S.; White, J. M.; Lópes, T.; Laird, S.; Wilson, D. J. D.; Barnard, P. J.; Hogan, C. F.; Francis, P. S. Chemistry – A European Journal 2014, 20, 3322.

[3] Doeven, E. H.; Barbante, G. J.; Kerr, E.; Hogan, C. F.; Endler, J. A.; Francis, P. S. Analytical Chemistry 2014, 86, 2727.

[4] Kerr, E.; Doeven, E. H.; Barbante, G. J.; Connell, T. U.; Donnelly, P. S.; Wilson, D. J. D.; Ashton, T. D.; Pfeffer, F. M.; Francis, P. S. Chemistry – A European Journal 2015, 21, 14987.

Page | 43


INVESTIGATING LIPOXYGENASE ACTIVITY ON TRILINOLEIN WITHOUT HYDROLYSIS USING

INEXPENSIVE SOYBEAN FLOURHoang-Anh T. Tu, Colin J. Barrow, Jacqui L. Adcock

Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences, Deakin University, Locked Bag 20000, Geelong, VIC 3220, Australia

[email protected]

Triacylglycerols (TAGs) are a natural form of biologically important omega-3 LC-PUFAs, which can be utilised as nutritional supplements in nutraceuticals and functional foods. Omega-3 fatty acids are essential for good health; they are anti-inflammatory and have numerous benefits, including in heart and mental health. Omega-3 LC-PUFAs are metabolised into bioactive lipid mediators by multiple enzymes, including lipoxygenase (LOX). Soybean flour is a rich source of LOX, especially LOX-2 which is unstable when purified and is not available commercially. We have used crude soybean flour as a stable source of LOX-2 which can react directly with LC-PUFA TAGs without hydrolysis (unlike commercially available LOX-1) to generate TAG hydroperoxides, with potentially higher bioactivity than the parent fatty acids.

Trilinolein was used as a model substrate for soybean flour lipoxygenase, and the reaction was optimised to maximise product yield (mono-, di- and tri-hydroperoxy trilinolein). To monitor the reaction, both normal and reversed phase HPLC methods were tested. Normal phase (silica and diol columns tested) was unsuitable as the substrate and mono-hydroperoxy product were poorly retained. Reversed phase with a C18 column resulted in a separation time of over 80 min with significant peak broadening for the substrate. However, a C8 column provided good separation within 25 min. Products were characterised by a range of analytical techniques, including: UV-vis absorbance spectroscopy to identify conjugation; 13C-NMR spectroscopy to determine enzyme preference for the sn-1,3 or sn-2 position on the glycerol backbone; GC-MS to determine position of hydroperoxy groups; and chiral HPLC to determine stereo-specificity of products. Buffer pH, reaction time and antioxidant concentration were found to affect the reaction significantly. This work offers a promising and inexpensive way to oxygenate TAGs directly without hydrolysis. This could be applied to natural oils to produce bioactive compounds for nutraceuticals and functional foods.

Page | 44


ASSESSMENT OF VOLATILE COMPONENT SAMPLING FOR FORENSIC INVESTIGATIONSLawrence D. Webb 1, Xavier Conlan 1, James Pearson2, John Kelleher2

1 Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences, Deakin University, Waurn Ponds, VIC, 3216

2 Victoria Police Forensic Services Department, Macleod, VIC, 3085

[email protected]

Fire debris analysis is performed on items of evidence suspected of containing volatile components such as petrol or diesel. This analysis is often used in cases of arson and is performed frequently at forensic centres around the world [1]. At Victoria Police a combination of passive headspace analysis using activated charcoal and gas chromatography is used to extract and analyse any volatiles that may be present in evidence. This study investigated several variables during the passive headspace analysis and examined the effects that the volume of ignitable liquid residue (ILR) present on a sample, sampling time and type of substrate has on the characteristic chromatographic peaks. It was found that the current methods employed by Victoria Police are robust enough to cater for the wide range of conditions that they encounter. Under all conditions the characteristic peak patterns were expressed to a degree in which the ILR could be identified. It was found however that the method is more suited to the recovery of lighter hydrocarbons, especially when low volumes and short sampling times were used. Preferential displacement of lighter hydrocarbons by heavier hydrocarbons was also observed when volumes were high and sampling time long.

[1] Pert, A.D., M.G. Baron, and J.W. Birkett, Review of Analytical Techniques for Arson Residues. Journal of Forensic Sciences (Wiley-Blackwell), 2006. 51(5): p. 1033-1049.

Page | 45


DRYLAB® OPTIMISED TWO-DIMENSIONAL HIGH PERFORMANCE LIQUID CHROMATOGRAPHY FOR

DIFFERENTIATION OF EPHEDRINE AND PSEUDOEPHEDRINE BASED METHAMPHETAMINE

SAMPLES

Luke M. Andrighetto 1, Paul G. Stevenson 1, Luke C. Henderson 2, Jim R. Pearson 3, Xavier A. Conlan 1

1 School of Life and Environmental Sciences, Deakin University, Waurn Ponds, 3216, VIC, Australia

2 Institute of Frontier Materials, Deakin University, Waurn Ponds, 3216, VIC, Australia 3 Victoria Police Forensic Services Department, Macleod, 3085, VIC, Australia

[email protected]

In-silico optimised two-dimensional high performance liquid chromatographic (2D-HPLC) separations of a model methamphetamine seizure sample are described, where an excellent match between simulated and real separations was observed. Targeted separation of model compounds was completed with significantly reduced method development time. This separation was completed in the heart-cutting mode of 2D-HPLC where C18 columns were used in both dimensions taking advantage of the selectivity difference of methanol and acetonitrile as the mobile phases. This method development protocol is most significant when optimising the separation of chemically similar chemical compounds as it eliminates potentially hours of trial and error injections to identify the optimised experimental conditions. After only four screening injections the gradient profile for both 2D-HPLC dimensions could be optimised via simulations, ensuring the baseline resolution of diastereomers (ephedrine and pseudoephedrine) in 9.7 min. Depending on which diastereomer is present the potential synthetic pathway can be categorised1.

Reference:

[1] Andrighetto, L. M., et al. (2014). "DryLab® optimised two-dimensional high performance liquid chromatography for differentiation of ephedrine and pseudoephedrine based methamphetamine samples." Forensic Science International 244: 302-305.

Page | 46


NANOPARTICLE ASSISTED LASER DESORPTION IONIZATION IN THE ANALYSIS OF DRUGS

Rachel S. West 1, G. Stewart Walker 1, K. Paul Kirkbride 1

1 Flinders University, GPO Box 2100, Adelaide, 5000, SA, Australia

[email protected]

Laser Desorption Ionization Mass Spectrometry (LDI-MS) is an analytical technique with a variety of advantageous qualities, these include, soft ionization, sensitivity, and rapid analysis. Such qualities are appealing for the analysis of forensically significant samples, such as drugs. LDI is, however, most commonly in conjunction with Matrix Assisted Laser Desorption Ionization (MALDI), where the matrix is a low mass, organic molecule capable of absorbing, and transferring, laser energy. MALDI is primarily used in for the analysis biological and polymeric, high mass, thermally unstable, samples. The adaptation of this technique to include low mass samples is made difficult due to matrix interference effects where the matrices are analysed along with the analytes of interest, often becoming the dominant peaks in the mass range of interest (<400 Da). This issue has led to the search for novel alternatives for assisting mediums, including a range of nanomaterials. This project explores the use of gold nanoparticles as an assisting medium in an LDI system for the analysis of a variety of drugs. Nanoparticles are novel materials that have a number of desirable qualities for such systems, including the absorption of light, stability and simple preparation.

Page | 47


DISCRIMINATION OF SINGLE NUCLEOTIDE POLYMORPHISM USING TOE-HOLD MEDIATED

STRAND DISPLACEMENT. R.A Fenati and A.V Ellis

Flinders Centre for Nanoscale Science and Technology, Flinders University, Sturt Road, Bedford Park, Adelaide, SA 5042, Australia

[email protected]

Single nucleotide polymorphism (SNP) is a prime example of genetic diversity found in DNA. A SNP is a single base variation in a DNA sequence that is commonly found in the population. In human identification and medical diagnostics precise SNP identification is important [1]. SNP genotyping has been used to identify genetic diseases. The SNP region of interest can be amplified from human DNA using polymerase chain reaction (PCR). PCR allows for the incorporation of fluorophores as well as the RNA basepair known as uracil. The DNA is then digested with the enzyme Uracil-DNA Glycolase (UDG) to remove the uracil and create a toehold. Resulting in the creation of a target strand containing a toehold that is hybridized to a shorter strand. Using a method known as toehold mediate strand displacement (fig 1), it is possible to discriminate between SNPs. A competing displacing strand (red) hybridises with the target strand (green) at the toehold and is able to displace the shorter strand (blue) into solution. Only fully complimentary DNA sequences are able to hybridise completely and displace the toehold strand, which allows for the discrimination of a SNP. This research is concerned with increasing the accuracy and efficiency of the toehold mediated strand displacement for improved identification of SNPs. By studying the effects of DNA intercalators, inserters and different fluorophore-quencher interactions might reveal additional ways to control the kinetics and migration efficiency of toehold mediated strand displacement.

Figure 1: Schematic for toehold mediated strand displacement used for SNP identification.

[1] Khodakov, D. A.; Khodakova, A. S.; Huang, D. M.; Linacre, A.; Ellis, A. V., Protected DNA strand displacement for enhanced single nucleotide discrimination in double-stranded DNA. Scientific Reports 2015, 5, 8721.

Page | 48


SIMULTANEOUS ANALYSIS OF 127 BASIC DRUGS IN FORENSIC CASES BY LIQUID CHROMATOGRAPHY

HYPHENATED WITH HIGH RESOLUTION ORBITRAP MASS SPECTROMETRY

Siti U. Mokhtar 1,2, Chadin Kulsing 1, Jalal T. Althakafy 1,3, Alex Kotsos 4, Olaf H. Drummer 4,5, Philip J. Marriott 1

1 Australian Centre of Research on Separation Science, School of Chemistry, Faculty of Science, Monash University, Clayton, VIC 3800, Australia.

2 Faculty of Chemical Engineering and Natural Resources, Universiti Malaysia Pahang, 26300 Pahang, Malaysia.

3 Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, 21955 Makkah, Saudi Arabia

4 Victorian Institute of Forensic Medicine, Southbank, VIC 3006, Australia5 Department of Forensic Medicine, Monash University, Clayton, VIC 3800, Australia.

[email protected]

In the present study, ultra-high pressure liquid chromatography coupled to an orbitrap mass spectrometer (UHPLCOrbitrap MS) was used for identification and quantification of 127 basic drugs simultaneously in biological samples (whole blood/plasma/serum). Samples were prepared by using liquid-liquid extraction (LLE) conducted using a trizma/isopropanol/butyl chloride buffer system. Reversed-phase separation employing a Thermo Accucore column (2.1 mm 50 mm) packed with 2.6 μm C18 particles was then performed under gradient elution with mobile phases consisting of acetic acid and aqueous-acetonitrile mixtures with the acetonitrile content ranging from 10 to 100% v/v. Compounds were detected with a high resolution Q Exactive Plus MS (resolution of 70,000 full width at half maximum) operated in full scan mode with narrow mass tolerance window (5 ppm) resulting in high selectivity and high mass accuracy (<5 ppm). Extracted ion chromatograms (XICs) provided analysis with acceptable linearity (r2) ranging from 0.99 to 1.00, low limits of detection (LOD) and low limit of quantification (LOQ). The lowest LOD obtained by using this instrument was found to be 0.02 ppb, observed for amitriptyline, chlorphenamine, hydroxyrisperidone, MDMA, methylamphetamine, nicotine, nortriptyline, zopiclone and zuclopenthixol. The developed method was applied to analyse drugs in 26 blood/plasma/serum samples from positive forensic cases. One forensic case, number 2535, revealed up to 30 positive drug residues. The method proved to be capable of reliable detection of drug analytes at trace level.

Page | 49


SPME-GC/MS AND ATR-FTIR ANALYSIS OF ORGANICS WITHIN AUSTRALIAN URANIUM ORE

CONCENTRATES FOR SOURCE ATTRIBUTION Tim Ditcham 1, Andrew Wotherspoon 2, Claire Lenehan 1,

Paul Kirkbride 1, Rachel S. Popelka-Filcoff

1 School of Chemical and Physical Sciences, Flinders University, Sturt Road, Bedford Park 5042, SA, Australia

2 Australian Nuclear Science and Technology Organisation, New Illawarra Road, Lucas Heights, 2234, NSW, Australia

[email protected]

The illicit trafficking of radioactive and nuclear material is a concerning contemporary issue faced by the international community, as there have been over 2000 confirmed incidents reported to the International Atomic Energy Agency since 1995. One important function of the nuclear forensics discipline is to identify the origin of the radioactive or nuclear material (source attribution), based upon key chemical, elemental and isotopic signatures. Uranium ore concentrates (UOCs) are of particular interest to nuclear forensics, as they contain >65% uranium by weight, and are a commodity traded internationally for the production of nuclear fuel. As the current capabilities of nuclear forensics result in an ambiguous determination of an unknown UOC’s provenance, necessitating the development of new signatures and analytical methodologies.

Recently, a sorptive extraction method has identified a number of organics within UOCs used in the solvent extraction (SX) process during their production [1]. SX utilises 2-3 different classes of organic compounds to purify the uranium: an extractant (a complexing agent), a diluent (often kerosene) and possibly a modifier (to increase the solubility of uranium-extractant complex in the organic phase). As SX processes are tailored to the environmental, chemical and economical concerns of each mine, with a variety of different organic compounds available, the organic profile of an unknown UOC may be used to identify its source.

Research described in this poster concerns the use of solid phase micro-extraction gas chromatography-mass spectrometry (SPME-GC/MS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) to investigate the organic content of Australian UOCs. ATR-FTIR analysis of organics extracted with dichloromethane, methanol and hexane enables a rapid screening of different classes of compounds used in SX, whereas SPME-GC/MS provides a specific identification of the different organic compounds present within these solvent extractions, which may be used to differentiate between UOCs from different sources.

References

[1] Kennedy, A. K.; Bostick, D. A.; Hexel, C. R.; Smith, R. R.; Giaquinto, J. M., Non-volatile organic analysis of uranium ore concentrates. Journal of Radioanalytical and Nuclear Chemistry 2013, 296.

Page | 50


DEVELOPMENT OF AN AUTOMATED SPECTROPHOTOMETRIC SYSTEM FOR MONITORING

OCEAN pH AND ALKALINITY.Vikashni Nand1

, Michael Ellwood1, Stephen Eggins1 and Bill Maher2

1 Research School of Earth Sciences, Australian National University, Canberra 0200, Australia.

2 Institute of Applied Ecology, Faculty of Applied Science, University of Canberra, Act 2601, Australia.

[email protected]

Since the nineteen fifties ocean acidification has led to a decline in pH of about 0.1 and decline in carbonate ion concentration ([CO3

=]) of ~70 mol kg-1. The decline in [CO32-] will

influence the ability of marine calcifiers to produce calcite and aragonite skeletons. Here we developed an automated spectrophotometric system to monitor changes in ocean pH and alkalinity in culture and field experiments in real-time. To determine seawater pH we used a purified pH-sensitive dye (m-Cresol Purple) and measured the proportions of the acid and base forms of the added dye . Using UV-vis. spectrometry seawater alkalinity was determined by adding a known amount of acid is added to a seawater sample to titrate all the bases present within the sample (HCO3

-, CO32-, B (OH) 4

-, etc.) after which a pH-sensitive dye is added the sample. The proportions of the acid and base forms of the added dye would be measured using a UV-visible spectrometer. pH and alkalinity measurements of an in-house standard using the automated pH-Alk system indicate that a precision of < ± 0.002 for pH and <± 10 mol/L for alkalinity thereby allowing the CO2 system to be constrained to ± 4 μatm. Field deployment of the system reveals variability in both pH and alkalinity at One Tree Island. These were associated with photosynthesis, respiration, calcification and dissolution processes.

Page | 51


THREE-STEP STACKING OF CATIONIC DRUGS BY FIELD-ENHANCED SAMPLE INJECTION,

SWEEPING, AND MICELLE TO SOLVENT STACKING IN CAPILLARY ZONE ELECTROPHORESIS

Wojciech Grochocki 1,2, Michał, J. Markuszewski2, Joselito, P. Quirino1

1 Australian Centre for Research on Separation Science, School of Physical Sciences-Chemistry, University of Tasmania, Churchill Avenue, 7005, TAS, Hobart, Australia

2 Departmen of Biopharmaceutics and Pharmacodynamics, Medical University of Gdańsk, Al. Hallera 107, 80-416 Gdańsk, Poland

[email protected]

The sensitivity enhancement factor (SEF) in field-enhanced sample stacking (FESI) is dependent on the conductivity ratio of background solution (BGS) to sample solution [1]. Here, the three-step stacking by FESI, sweeping, and micelle to solvent stacking (MSS) of cationic drugs in capillary zone electrophoresis (CZE) is presented to overcome the limitation of FESI. The three-step stacking was as follows. For FESI, the sample was introduced electrokinetically by applying high voltage at positive polarity (10 kV) and long zone of stacked cationic analytes was created. For sweeping, the FESI focused analytes were swept by negatively charged sodium dodecyl sulfate (SDS) micelles that were injected by replacing sample vial with micellar solution vial and applying high at negative polarity (-10 kV). For MSS, 30% acetonitrile (ACN) was used for effective electrophoretic mobility reversal of cationic analytes. A short plug of ACN was injected hydrodynamically after sweeping step. Applying high voltage at positive polarity caused migration of micelle bounded analytes towards inlet end of the capillary. When they reached the ACN zone, the SDS micelles collapsed and released transported analytes. Finally, accumulated analytes were separated by CZE. Under the experimental conditions studied, the SEF (vs typical injection in CZE) range of FESI using a conductivity ratio of 10, 100, and 1000 (sample diluent with conductivity 10, 100, and 1000x lower than the BGS, respectively) was 5-6, 33-50, and 272-393, respectively. The SEF range of three-step stacking was 308-891, 2188-6463, and 3088-6499, correspondingly. The SEF enhancement factor due to three-step stacking (SEF of three-step stacking divided by SEF of FESI) was from 11-161. Analytical figures of merit including linearity, LOD (S/N = 3), and repeatability (intraday and interday) were determined. Moreover, sample matrix effect was studied using acetone treated plasma sample.

Reference:[1] Chien, R. L.; Burgi, D. S. On-Column Sample Concentration Using Filed Amplification in CZE Anal Chem 1992, 6, 489A-496A

Page | 52


Page | 53


Poster AbstractsWednesday 9th December

Page | 54


PORTABLE IR-LED BASED ATMOSPHERIC MONITORING: AUTOMATED DATA HANDLING OF

LARGE DATA STREAMS Ansara Noori 1, Mirek Macka 1, Arko Lucieer 2, John Parry 3

1 School of Physical Sciences - Chemistry, University of Tasmania, TAS, Australia2 School of Land and Food, University of Tasmania, TAS, Australia

3Central Science laboratory, University of Tasmania, TAS, Australia

[email protected]

For analytical platforms where the sample property can change at a fast rate, such as in case of atmospheric monitoring, a rapid digital sampling and analysis rates are required. This is well satisfied with optical detection (analysis) methods like infra-red (IR) photometry, followed by adequately fast electronics and data handling. Although IR spectral region photometry based gas detection is a well-established technique, with current developments in portable sensing instruments, designing small low-cost low power consumption analytical platforms compatible with portable and remote analysis formats present a number of challenges. One of them is processing of continuous and live rapid data streams. Such low-cost, small-size-weight and low-power analytical platforms are desirable in a number of in-field deployment modes including human carried devices and on-board of micro-unmanned aerial vehicles (micro-UAVs).

Online or live data collection is desired for the analysis of the chemical which is aimed from the remote platform; while automation of data acquisition is substantial where huge amount of data producing within a millisecond need to be handled. Programmable micro controllers with high sampling frequency and flexibility in using programs required for custom designed data acquisition are noteworthy. In this work we use an open source single-board micro-computer with fast analogue-to-digital (A ↔ D) converter “Red Pitaya” to meet the above requirements to collect real-time data and process it using dedicated program codes.

Page | 55

mailto:[email protected]


THE USE OF 3,4-HPO LIGANDS IN THE DEVLOPMENT OF A MICROFLUIDIC PAPER-BASED

ANALYTICAL DEVICE (µ-PAD) FOR THE DETERMINATION OF IRON IN NATURAL WATERS

Chelsea R. Bassett1, Raquel B.R. Mesquita2, Maria Rangel3, Spas D. Kolev1

1 School of Chemistry, The University of Melbourne, VIC, 3010, Australia2 Escola Superior de Biotecnologia, Universidade Católica Portuguesa, 4202-401 Porto,

Portugal3 REQUIMTE-UCIBIO, Instituto de Ciências Biomédicas de Abel Salazar, Universidade do

Porto, 4050-313 Porto, Portugal

[email protected]

Microfluidic paper-based analytical devices (µ-PADs) have, in recent years, provided a novel approach for conducting inexpensive, on-site analyte determination which is easily used by untrained operators. The small dimensions, minimal reagent/sample consumption, low cost, ease of operation and favourable analytical performance make µ-PADs attractive for rapid on-site analysis in many fields, namely for environmental water monitoring.

Iron is an essential micronutrient in the environment. It is necessary to monitor the iron content in waters as high concentrations of iron have aesthetic (i.e. colour, taste) and technical (i.e. scaling, staining, pipe damage) implications [1]. This work explores the use of 3-hydroxy-4-pyridinone (3,4-HPO) chelators as chromogenic reagents to develop a µ-PAD for the determination of iron in natural waters. These chelators have been used previously in sequential injection approaches [2] for the iron determination as they are nontoxic alternatives to the traditional and highly toxic chromogenic species such as thiocyanate, 1,10-phenanthroline, bathophenanthroline [3]. They are also reportedly more selective than their traditional counterparts [2] which is a necessary feature to maintain the simplicity of the µ-PAD and to be able to apply it to complex environmental water matrices.

References[1] U.S. Environmental Protection Agency. Secondary drinking water regulations: guidelines for nuisance chemicals. (accessed 11/11/2015).

[2] Mesquita, R. B. R.; Suárez, R.; Cerdà, V.; Rangel, M.; Rangel, A. O. S. S., Exploiting the use of 3,4-HPO ligands as nontoxic reagents for the determination of iron in natural waters with a sequential injection approach. Talanta 2013, 108, 38-45.

[3] Marczenko, Z.; Balcerzak, M., Separation, preconcentration and spectrophotometry in inorganic analysis. Elsevier: 2000

Page | 56


ISOTOPIC ANALYSIS OF GAMMA-HYDROXYBUTYRIC ACID (GHB), SYNTHESISED

FROM ONE OF ITS PRECURSORS GAMMA-AMINOBUTYRIC ACID (GABA)

Claire Szuster 1, K. Paul Kirkbride 1

1 Flinders University, Bedford Park, 5042, SA, Australia

[email protected]

Gamma-aminobutyric acid (GABA) is a commonly used bodybuilding supplement, it is used to increase muscle mass and decrease fat [1, 2]. GABA is a common precursor for the illicit manufacture of Gamma-Hydroxybutyric Acid (GHB). GHB is a date rape drug that is becoming more common in the party scene, and especially common in drug facilitated sexual assaults (DFSA) [3]. GHB is becoming more common in the party scene due to its ease of administration, as a colourless liquid.

This study analyses the carbon isotope ratios in GABA from various suppliers and GHB produced from these sources to see if chemical links can be established. The isotope ratios were determined using Elemental Analysis/Isotope Ratio Mass Spectrometry (EA/IRMS) as well as Gas Chromatography/ Combustion/ Isotope Ratio Mass Spectrometry (GC/C/IRMS) to analyse both GABA and GHB. The results of this study show that this approach can be used by law enforcement agencies in regards to GHB production and distribution.

References

1. South, C. Clayton's Health Facts: GABA. 2001 [cited 2015 20th October ]; Available from: http://www.bodybuilding.com/fun/southfacts_gaba.htm.

2. House, B. and S. Schedule. Gamma-aminobutyric acid (GABA). 2011 [cited 2015 10th October]; Available from: http://www.westerlynaturalmarket.com/ns/DisplayMonograph.asp?StoreID=QWCSN3N89ASR2JS000AKHMCCQAB04FN2&DocID=bottomline-gaba.

3. Saudan, C., et al., Carbon isotopic ratio analysis by gas chromatography/combustion/isotope ratio mass spectrometry for the detection of gamma-hydroxybutyric acid (GHB) administration to humans. Rapid Communications in Mass Spectrometry, 2007. 21(24): p. 3956-3962.

Page | 57

http://www.westerlynaturalmarket.com/ns/DisplayMonograph.asp?StoreID=QWCSN3N89ASR2JS000AKHMCCQAB04FN2&DocID=bottomline-gaba

http://www.westerlynaturalmarket.com/ns/DisplayMonograph.asp?StoreID=QWCSN3N89ASR2JS000AKHMCCQAB04FN2&DocID=bottomline-gaba

http://www.bodybuilding.com/fun/southfacts_gaba.htm


LAB-ON-A-CHIP MASS SPECTROMETRY TOOLS FOR TESTING ILLICIT DRUGS

Eliza C. Moule 1, K. Paul Kirkbride 1, Nicolas Voelcker2, Taryn Guinan2

1Flinders University, Sturt Rd Bedford Park, 5042, SA, Australia2 University of South Australia, Mawson Lakes Boulevard Mawson Lakes, 5095, SA,

Australia

[email protected]

The emergence of new mass spectrometry technology has driven the development of nanostructured substrates to improve their performance. In particular, there is a growing interest in the improvement of point of collection drug testing employed at roadsides and in workplaces. Currently, this testing is done using immunoassay ‘reactive’ testing, which have relatively high false positive rates, which. These tests also provide presumptive results only, which require confirmatory testing in toxicology labs. This is low-throughput, laborious and time consuming process that requires chromatographic methods to separate the drug of interest from the complex biological matrix.

Recent work has shown the effectiveness of Surface Assisted Laser Desorption Ionisation (SALDI) techniques coupled with nanostructured substrates such as porous silicon (pSi) in the detection of illicit drugs in oral fluid [1]. These pSi substrates are able to easily integrate into Matrix Assisted Laser Desorption Ionisation (MALDI) instrumental systems already installed, and can give de-convoluted mass spectra not usually seen for MALDI analysis of low molecular weight compounds. On top of this, the surface chemistry of these substrates can be easily manipulated to facilitate a rudimentary chromatographic process to isolate the analyte of interest [2]. This work aims to build on the previous research to develop and optimise a number of surfaces with the ability to improve sensitivity, selectivity and ionisation efficiency of illicit drugs in oral fluid, urine and sweat. The use of an ambient chemical ionisation system recently developed by Perkin Elmer will be investigated as a potential analysis system for these ‘lab-on-chip’ devices, which would allow for high-throughput sample analysis with little sample preparation.

References

1. Guinan, T., et al., Rapid detection of illicit drugs in neat saliva using desorption/ionization on porous silicon. Talanta, 2012. 99: p. 791-798.

2. Guinan, T., Surface Assisted Laser Desorption Ionisation for Forensic Applications, in Mawson Institute Division of Information Technology, Engineering and Environment. 2014, University of South Australia: South Australia.

Page | 58


INVESTIGATIONS INTO THE FATE OF EXPLOSIVES IN SOIL

Holly A. Yu 1,2, David A. DeTata 3 and Simon W. Lewis 1,2

1 Department of Chemistry, Curtin University, GPO Box U1987, Perth, 6845, WA, Australia2 Nanochemistry Research Institute, Curtin University, GPO Box U1987, Perth, 6845, WA,

Australia3 Forensic Science Laboratory, ChemCentre, Manning Road, Bentley, 6102, WA, Australia

[email protected]

Explosives residues in soil may be a useful source of evidence following the detonation of an improvised explosive device, such as a vehicle bombing. Soil samples collected from the vicinity of an explosion scene will often be stored for a period of time prior to their analysis, yet explosives residues in collected soil samples are susceptible to rapid degradation or transformation. It is therefore important to investigate the degradation of explosives in soil under a range of conditions in order to maximise their stability prior to a soil sample’s extraction and analysis. Previous research has investigated this phenomenon by spiking blank soil samples with solutions of explosives, though very little research has examined the degradation of explosives in soil which have been deposited via an actual detonation process. However, it is known that detonations can cause soil fracturing, exposing fresh mineral surfaces in the soil which are likely to affect explosives degradation rates and mechanisms, so further research examining the degradation of explosives in fractured soil following an actual detonation would be of benefit.

This work therefore aims to investigate the degradation of explosives deposited in soil following a controlled detonation process. A range of explosives deposition processes and storage conditions will be trialled throughout this work. Ultimately this research aims to answer a number of research questions including: which storage condition, of those trialled, is the best for mitigating explosives degradation in soil; what is the pattern of PETN degradation in soil; do car bombs cause soil fracturing; what effect does a soil’s composition have on the rate of degradation of explosives; and does the degradation of explosives in laboratory-spiked blank soils adequately mimic their degradation in soils fortified with explosives via an actual detonation process?

Page | 59


FORENSIC IDENTIFICATION AND DISCRIMINATION OF GUNSHOT RESIDUE

Kelsey E. Seyfang 1, K. Paul Kirkbride 1, Hilton Kobus1, Rachel Popelka-Filcoff 1

1 Flinders University, Sturt Road, Bedford Park 5042, SA, Australia

[email protected]

Guns were used in crimes amassing over twenty-four thousand victims in Australia between 1995 and 2012, including 859 homicides [1]. When a gun is fired, a bullet and a mixture of vapours and particles are expelled from the weapon. This mixture, known as gunshot residue (GSR), consists of organic and inorganic compounds that when expelled from the weapon land on surroundings surfaces, including the clothes, hair and skin of the shooter and any close bystanders. Gunshot residue (GSR) detection is critical for forensic scientists trying to determine whether someone was present during a shooting event.

The current method of identifying GSR involves detecting lead, barium and antimony in a single particle. In Australia, most firearms are 0.22 rimfire calibre weapons, of which, up to 84% do not contain primer sources of antimony[2]. This calibre also typically contains powdered glass as a frictionator, instead of the more common calcium silicide. This can make the identification of GSR difficult. This project’s focus is on improving the detection of and discrimination between samples of GSR through the potentially highly characteristic glass particles fused with lead and barium (glassy GSR) [3, 4]. The probative value of these particles will be assessed by investigating potential sources of similar particles, such as from brake pads or fireworks. The variation of glass and glassy GSR in ammunition across the Australian market will be assessed, focussing on 0.22 calibre weapons, allowing for the comparison of GSR on a suspect and from a putative source. A method of including glassy GSR in general analysis will be determined for forensic laboratories.

References:

1. Australian Bureau of Statistics, Weapon use in violent crime, by victims per year (n) 1995-2012, in Facts & Figures online data tool, A.I.o. Criminology, Editor. 2013: Canberra, Australia.

2. Wrobel, H.A., J.J. Millar, and M. Kijek, Identification of Ammunition from Gunshot Residues and Other Cartridge Related Materials-A Preliminary Model Using .22 Caliber Rimfire Ammunition. Journal of Forensic Sciences, 1998. 43(2): p. 5.

3. Coumbaros, J., et al., Characterisation of 0.22 caliber rimfire gunshot residues by time-of-flight secondary ion mass spectrometry (TOF-SIMS): a preliminary study. Forensic Science International, 2001. 119(1): p. 72-81.

4. Collins, P., et al., Glass-containing gunshot residue particles: A new type of highly characteristic particle? Journal of Forensic Sciences, 2003. 48(3): p. 538-553.

Page | 60


USING CHROMATOGRAPHIC TECHNIQUES TO STUDY RETENTION PROCESSES ON POROUS GRAPHITIC CARBON STATIONARY PHASES

Kirsteen R. Smith 1, Xavier A. Conlan 1, Paul G. Stevenson1

1 Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences,

Deakin University, 75 Pigdons Road, 3216, VIC, Australia

[email protected]

In order to fully realise the potential of graphitic based structures for separation science, applications of some key fundamental aspects need to be better understood. Comparative studies of a porous graphitic carbon column, a C18 monolith column and a C18 particle packed column were carried out to determine the separation processes.

A selected set of compounds of planar and 3D aromatic structures with various functional groups were investigated using a variety of chromatographic techniques including peak parking and adsorption isotherms to study the retention processes between analytes and stationary phase. Investigations into the re-equilibration requirements of this surface were also completed.

Preliminary results predict the porous graphitic carbon surface has a high affinity for aromatic compounds due to planar π-π interactions between the stationary phase and the analytes. A comparative study was completed to investigate the differences of these interactions to C18 particle packed and monolithic support materials.

This study displays the importance of the planar structure and the polarity of side end groups on this type of separation mechanism of the porous graphitic surface. These results are better able to inform the optimisation of separations on porous graphitic carbon chromatography columns for commercial applications.

Page | 61


VANADIUM PHYTOTOXICITY: VANADIUM AND NUTRIENT DYNAMICS

Maddumage D. E. J. Abeywardane 1, Suzie Reichman 1, Jeff Hughes2

1 School of Civil, Environmental and Chemical Engineering, RMIT University, Melbourne, 3000, VIC, Australia

2 School of Applied Sciences, RMIT University, Melbourne, 3000, VIC, Australia

[email protected]

Vanadium is a ubiquitous element in nature. There has been an exponential rise of vanadium in the biosphere in the last half century due to increasing consumption of fossil fuel sources [1, 2]. Vanadium toxicity in plants has been observed as an overall reduction in growth yield but symptom development process and the underlying mechanisms are not yet fully understood.

With chelator buffered nutrient solutions using sodium vanadate as a vanadium source at pH 6, we have shown that vanadium can significantly reduce the overall plant growth using Phaseolus vulgaris (common beans) and Triticum aestivum (wheat) as test species. In common beans, vanadium caused a 50% reduction in plant dry yield above 64 µM. In wheat, vanadium only caused a 4% reduction of total dry mass in a solution of 64 µM but the mass reduction increased above 40% in a 256 µM solution. Vanadium predominantly affected the growth of the root system by sharply reducing secondary and higher order lateral branching. Reduction in root growth was accompanied by a stunted aerial growth, malformed and wrinkled leaves, chlorosis and necrosis. Thus, vanadium appears to interfere with the uptake of other vital nutrients to plants including iron, magnesium, calcium and phosphorus and such further investigations are underway. Species vary greatly in their ability to tolerate vanadium toxicity. A separate experiment will be carried out to examine the effect of vanadium on seed germination and radicle elongation across a range of species in order to further investigate the effect of species selection on vanadium phytotoxicity. As revealed by our preliminary experiments, vanadium affects legume and Rhizobium symbiosis thereby affecting plant nitrogen dynamics. We are conducting an experiment to examine how vanadium affects nodulation parameters and tissue nitrogen levels in common beans.

References

[1] Barker A. V.; Pilbream, D. J. Handbook of Plant Nutrition; Taylor & Francis: 2006; pp 585-597.

[2] Morrel B. G.; Lepp, N.W.; Phillip D A. Vanadium Uptake by Higher Plants: Some Recent Developments. Environmen. Geochem. Health. 1986, 8, 14 – 18.

Page | 62



ADVANCED PULSED ELECTROCHEMICAL DETETCTION OPTIONS FOR MICROFLUIDIC AND

PAPER FLUIDIC PLATFORMSMuhammed Ariful Islam 1, Mirek Macka 1, Pavel Nesterenko 1, Brett Paull 1,

Li Yan 1

1 School of Physical Sciences and Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75, Hobart 7001, TAS, Australia

[email protected]

Electrochemical detection (ECD) offers an advantage as a sensitive detection methods for applicable electroactive analytes in various flow-based analytical methods, including capillary electrophoresis and chromatographic methods. Several advantages, such as to modify detection selectivity, low cost of instrumentation and potential to miniaturization, make ECD an ideal detection for miniaturised fluidic analytical systems. Even so, none of these methods is truly universal, highly sensitive and robust. ECD has become increasingly popular because of the success of most widely used mode pulsed electrochemical detection (PED), for aqueous based separation for its capability of highly selectivity and sensitive detection. Additionally, PED techniques has the potential in terms of positive and negative pulses for oxidative desorption of adsorbed species and also continuously precondition the surface of the electrode to produce a reproducible and clean electrode surface during the measurement cycle [1]. In modern pulsed formats, pulsed amperometric detection (PAD) has proven itself as a highly sensitive and reliable method but it is not universal. Compared to the PAD, in contrast pulsed potentiometric detection (PPD) can be universal because it has capability to detect any species [2] but often lacks the stability and robustness especially in miniaturised formats. Therefore, the emphasis of this research is on investigating novel pulsed electrochemical methods especially PPD and/or in combination with PAD techniques, conducted concurrently in one detection cell in miniaturised separation platforms. This will provide a powerful universal detection as it was case for CE [1] and will be investigated for pressure driven LC methods, as well as in microfluidic chip and paper fluidic formats. The resulting advanced combined PED methods are expected to benefit portable analytical devices.

References:

[1] Zakaria, P.; Macka, M.; Gerhardt, G.; Haddad, P.R. Pulsed potentiometric detection in capillary electrophoresis using platinum electrodes. Analyst. 2000, 125, 1519-1523.

[2] Richard, P. B. Recent advances in electrochemical detection in capillary electrophoresis. Electrophoresis 2000, 21, 4017-4028.

Page | 63


CLASSIFICATION OF ORGANIC MATERIALS WITH LASTER INDUCED BREAKDOWN SPECTROSCOPY

Sally L. Doolette1, 3, Jamie Quinton1, 3, Benjamin L. Rogers1, 2

1 Flinders University, Bedford Park, 5042, SA, Australia2 Defence Science and Technology Group, Edinburgh, 5111, SA, Australia

3 Centre of Expertise in Energetic Materials Flinders University, Bedford Park, 5042, SA, Australia

[email protected]

Laser Induced Breakdown Spectroscopy, or LIBS as it is commonly known, was introduced as a novel spectroscopic technique in the 1960’s after the pulsed ruby laser was developed in 1960 [1]. The LIBS method, in terms of its techniques and applications, continued to grow from this point on.

LIBS is an atomic emission spectroscopy method that is able to rapidly analyse in-site samples of solid, liquid or gaseous forms over a wide spectral range [2]. Over the past few decades LIBS has been employed in many fields, including but not limited to use in industrial, biomedical, geological, archaeological and environmental applications [3] as well as in energetic materials research [4]. LIBS has shown much promise in qualitatively analysing organic materials, which is of interest to the Defence Science and Technology Group (DST Group) in terms of organic energetic material identification.

The optimal parameters for organic material identification using the newly custom-built LIBS system at DST Group are investigated. Single Pulse (SP) and Double Pulse (DP) modes of laser operation, the inter-pulse delay of DP LIBS, the gate delay of the spectrometer and the use of an inert atmosphere to optimise conditions are reported. The mathematical methods Principal Component Analysis (PCA) and Cluster Analysis are used to investigate the feasibility of the DSTO LIBS system to correctly classify classes of organic samples. Types of plastic samples were looked at and the proficiency of clustering seen are discussed.

[1] Cremers, D. A.; Radziemski, L. J. Handbook of Laser-Induced Breakdown Spectroscopy. John Wiley & Sons Ltd. 2006, England.

[2] Singh, J. P.; Thakur, S. N. (Eds.) Laser-Induced Breakdown Spectroscopy. Elsevier Science. 2007.

[3] Anzano, J.; Bonilla, B.; Montull-Ibor, B.; Casas-Gonzalez, J. Rapid characterisation of analgesic pills by laser-induced breakdown spectroscopy (LIBS). Med. Chem. Res. 2009, 18, 656-664.

[4] Gottfried, J. L.; De Lucia, F.C.; Munson, C.A.; Miziolej, A.W. Strategies for residue explosives detection using laser-induced breakdown spectroscopy. J. Anal. At. Spectrom. 2008, 23, 205-216.

Page | 64



THE DEGRADATION OF PSEUDOEPHEDRINE IN SOIL DUE TO MICROBIAL ACTION

Simone A. Madaras 1, Claire E. Lenehan 1, K. Paul Kirkbride 1

1 School of Chemical and Physical Science, Flinders University, Bedford Park, 5042, SA, Australia

[email protected]

This project aimed to identify the metabolites of pseudoephedrine resulting from microbial action in soil. Pseudoephedrine is the most common precursor to illicit methamphetamine, and waste products containing it are often discarded in soil to hide evidence. Pseudoephedrine is known to decompose in soil as a result of microbial action but its metabolites have not been identified. The profile of metabolites of pseudoephedrine residues in soil can be used in forensic investigations to contribute to the prosecution of methamphetamine manufacturers, especially when pseudoephedrine has been completely degraded, while identifying any environmental hazards associated with methamphetamine manufacture. Authorities can use the knowledge of pseudoephedrine degradation in soil as evidence for the prosecution of criminals in methamphetamine manufacture-related criminal cases. Compost and garden soil, as well as lawn dressing, were spiked with pseudoephedrine and left over a period of two months. The soil was analysed using ultra high performance liquid chromatography coupled with mass spectrometry. Compost soil showed the most pseudoephedrine degradation as a result of microbial action, while lawn dressing showed a very small amount of degradation. Garden soil showed almost no signs of pseudoephedrine degradation. Degradation metabolites were also detected using mass spectrometry.

Page | 65


PREDICTION OF RETENTION TIMES IN REVERSED-PHASE LIQUID CHROMATOGRAPHY BASED ON CHEMICAL

STRUCTURES OF ANALYTESYabin Wen 1, Mohammad Talebi 1, Ruth Amos 1, Robert Shellie 1, Roman

Szucs 2, Christopher A. Pohl 3, John W. Dolan 4, Paul R. Haddad *1

1 Australia Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75, Hobart 7001, Australia

2 Pfizer Global Research and Development, Sandwich, UK3 Thermo Fisher Scientific, Sunnyvale, CA, USA

4 LC Resources, Walnut Creek, CA, USA

[email protected]

The chemical structures of analytes were used to predict the retention times of reversed-phase liquid chromatography in different conditions and columns. Quantitative structure-retention relationship (QSRR) is capable of relating chromatographic retention time to the chemical structure of a solute. A QSRR approach is carried out whereby molecular modelling is utilised to generate molecular descriptors of analytes based on their chemical structures. A moderately sized retention training database which comprise 112 compounds was established and a total of 666 descriptors were calculated and exported from the optimized structures of the molecules using DRAGON software for each compound. From the large number of descriptors generated, the most relevant descriptors were determined using genetic algorithm (GA)-partial least squares (PLS) regression approach for feature selection. Then the mathematical relationship between selected descriptors and measured retention times is generated for a test set of solutes, and the final relationship will be used to predict the retention time for new compounds only based on their chemical structures. In previous pilot study, very good correlation has been achieved between predicted and observed retention time, it is also expected to achieve a good correlation for new solutes.

Page | 66


APPROACHES TO PORTABLE ANALYSIS OF BIOANALYTES USING MICRO- AND PAPERFLUIDIC

PLATFORMS UTILISING ENZYMATIC ACTIVITIESMónica N. Alves 1, Pavel Nesterenko 1, Brett Paull 1, Mirek Macka 1

1 Australian Centre for Research on Separation Science, School of Chemistry, University of Tasmania, Sandy Bay, 7005, TAS, Australia

[email protected]

The desire for immediate chemical analysis is one of the driving forces for the development of

portable instruments [1]. Analysing samples within minutes using extremely small, compact and

inexpensive instrumentation is useful in many applications such as for point-of-care devices,

personalized medicine, or even for molecular analysis and monitoring bioprocesses in living cells [2].

This study focuses on portable analysis of bioanalytes using micro- and paperfluidic technologies

utilizing different approaches to achieve analytical selectivity and specificity. Enzymatic activities

occurring in the human liver will be a significant part of the project. A number of therapeutic drugs with

different structures and mechanisms of action have been reported to undergo metabolic activation by

phase I or phase II drug metabolizing enzymes. The bioactivation gives rise to metabolites or reactive

intermediates, which confer covalent binding to various cellular macromolecules such as proteins or

DNA [3]. The covalent binding and formation of drug-protein and drug-DNA adducts are generally

considered to be related to drug toxicity and carcinogenicity, respectively [4]. These drugs comprise

anti-HIV agents, anti-bacterial agents, anti-cancer drugs, analgesics, cardiovascular drugs,

antipsychotics, antiepileptic drugs, inhalational anaesthetics, immunosupressants, nonsteroidal anti-

inflammatory drugs, and steroids and their receptor modulators [5]. The aim of this project is to

design, develop and optimize innovative micro- and paperfluidic devices for miniaturised biochemical

assays trough enzyme immobilisation. The methods used should be simple, rapid and applicable to a

wide variety of enzymes. The portable analysis system will allow detecting, identifying, and separating

reactive metabolites resulting from sequential steps of drug metabolism. Further analysis of

metabolite and reactive intermediates as well as detection of drug-DNA/protein adducts will also

clarify specific metabolic pathways of drugs bioactivation.

References

1. Zhang, J.; Yan, S.; Yuan, D.; Alici, G.; Nguyen, N.-T.; Warkiani, M. E.; Li, W., Fundamentals and applications of inertial

microfluidics: a review. Lab Chip 2015.

2. Whitesides, G. M., The origins and the future of microfluidics. Nature 2006, 442 (7101), 368-373.

3. Guengerich, F. P.; MacDonald, J. S., Applying mechanisms of chemical toxicity to predict drug safety. Chem. Res. Toxicol.

2007, 20 (3), 344-369.

4. Caixas, U.; Antunes, A. M.; Marinho, A. T.; Godinho, A. L.; Grilo, N. M.; Marques, M. M.; Oliveira, M. C.; Branco, T.;

Monteiro, E. C.; Pereira, S. A., Evidence for nevirapine bioactivation in man: searching for the first step in the mechanism of

nevirapine toxicity. Toxicology 2012, 301 (1), 33-39.

5. Funke, M.; Buchenauer, A.; Schnakenberg, U.; Mokwa, W.; Diederichs, S.; Mertens, A.; Müller, C.; Kensy, F.; Büchs, J.,

Microfluidic biolector—Microfluidic bioprocess control in microtiter plates. Biotechnol. Bioeng. 2010, 107 (3), 497-505.

Page | 67


Oral AbstractsMonday 7th December

Page | 68


EXTRACTION AND SEPARATION OF LANTHANIDES USING POLYMER INCLUSION MEMBRANES (PIMs)Charles F. Croft, M. Inês G.S. Almeida, Robert W. Cattrall , Spas D. Kolev

School of Chemistry,, The University of Melbourne, Parkville 3010, VIC, Australia

[email protected]

Using pure lanthanides is crucial to the development and quality of modern day technology where they are used to tune the electronic and optical properties of materials. Lanthanides have applications as glass additives, catalysts, screen phosphors, magnets in computer hard drives and also in green energy technology such as wind turbines and batteries in electric cars 1. Lanthanides differ only in the number of electrons in their f orbitals, and have very similar physicochemical properties making its separation difficult 2. Separation is currently conducted using solvent extraction, which causes health and environmental hazards associated with the large quantities of organic solvents used 3. Separation based on the use of polymer inclusion membranes (PIMs) is a greener alternative to solvent extraction as the use of organic solvents is nearly eliminated and the quantity of extractant used is very small 3b. PIMs are a relatively new type of liquid membrane where the extractant is incorporated into the polymer backbone of the membrane. The extractant di-(2-ethylhexyl)phosphoric acid (D2EHPA) has already been successfully used to separate lanthanides in commercial solvent extraction and has been used for the manufacturing of PIMs with PVC-based backbone 3. Current work with D2EHPA/PVC PIMs demonstrates that they can extract lanthanide ions and that separation of the light, middle and heavy lanthanides is possible through manipulation of feed solution acidity. Research will be conducted to identify the stoichiometry and kinetics of lanthanide extraction into D2EHPA-based PIMs and to optimise the back-extraction of the lanthanide cations from the membranes.

References

1. Binnemans. K; Jones. P. T; Blanpain. B; Gerven. T. V, Recycling of rare earths: a critical review. Journal of Cleaner Production 2013, 51, 1-22.2. Atkins. P; Overton. T; Rouke. J; Weller. M; Armstrong. F; M, H., Shriver and Atkins Inorganic Chemistry. Oxford University Press: New York, 2011.3. (a) Cox, M.; Rydberg, J., Solvent Extraction Principles and Practice. 2nd ed.; Marcel Dekker, Inc: New York, 2004; (b) Almeida, M. I. G. S.; Cattrall, R. W.; Kolev, S. D., Recent trends in extraction and transport of metal ions using polymer inclusion membranes. Journal of Membrane Science 2012, 415-416, 9-23.

Page | 69


A NEW INNOVATIVE SPECTROPHOTOMETRIC METHOD FOR DETERMINATION OF CONCENTRATION RATIOS IN

BINARY MIXTURESFotouh R. Mansour 1,2

1 Australian Centre for Research on Separation Science (ACROSS), School of Chemistry, University of Tasmania, Private Bag 75, 7001, Tasmania, Australia

2 Department of Pharmaceutical Analytical Chemistry, Tanta University, Egypt, 31111

[email protected]

The number of multicomponent products has exponentially increased in the pharmaceutical market due to higher patient compliance, less adverse events, quicker responses, and synergistic effects [1]. Different techniques have been employed in quality control laboratories for simultaneous determination of active ingredients in such multicomponent dosage forms [2]. A new innovative method is developed to determine the concentration ratio in binary mixtures by determining the wavelength of intersection in the first derivative of the gross curve. This relationship can be applied if the part of the UV spectrum of substance Y, that intersects with the overlaid spectra of substance X is straight.

By plotting the intersection wavelength against the concentration ratio (

C xC y ), a straight line

was obtained with a co-efficient of determination (r) equal 0.996. To validate the method, the UV spectrum of 10 mg L-1 cinnarizine (CNZ) was recorded and the raw data were obtained and used to calculate the spectra of 12, 14, 16 mg L-1. The UV spectrum of 10 mg L-1

nicergoline (NCG) was also recorded and overlaid with the spectra of CNZ. The intersection wavelengths were determined for each concentration and plotted against the concentration ratio of CNZ to NCG. A linear relationship was obtained with a co-efficient of determination of 0.99. This method can be applied for the estimation of biomarkers for diagnosis of some disorders such as tuberculosis, oxidative stress, atherosclerosis, gastric atrophy, and malignant melanoma.

References:

1 Gindy, A. EL and Hadad, G.M. Chemometrics in Pharmaceutical Analysis: An Introduction, Review, and Future Perspectives. J. AOAC Int. 2012, 95, 609–623

2 Bosch Ojeda, C. and Sanchez Rojas, F. Recent applications in derivative ultraviolet/visible absorption spectrophotometry: 2009–2011. Microchem. J. 2013, 106, 1–16

Page | 70


ELEMENTAL AND MOLECULAR PROFILING OF LICIT, ILLCIT AND NICHE TOBACCO

K. Quayle 1,3*, G. Clemens 1, T. Garcia Sorribes 1, H. M. Kinvig 1 and M. J. Baker 1,2*

1 Centre for Materials Science, Division of Chemistry, School of Forensic & Investigative Sciences, University of Central Lancashire, Fylde Road, Preston U. K.

2 West CHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathederal Street, Glasgow U.K.

3 Centre for Regional and Rural Futures, Deakin University, Locked bag 20000, Waurn Ponds, Geelong, Australia.

Email: [email protected]

Tobacco plants are renowned for their ability to preferentially uptake heavy metals and accumulate over 4,000 chemicals throughout cultivation, with many of these being recognised by the International Agency for Research on Cancer (IARC) branch of the World Health Organization (WHO) as human carcinogens 1. Sustained tobacco use and addiction is attributed to the alkaloid nicotine being ingested into the blood steam, allowing for the stimulation cholinergic receptors within the Central Nervous System (CNS), causing the rapid release of Dopamine 2. Prolonged exposure to tobacco has been repeatedly linked to adverse health effects and the development of life threatening illness such as cancer, cardiovascular disease and strokes, effects which are enhanced due to the poor grade unregulated cultivation of the tobacco and mediocre delivery systems found within tobacco of illicit or niche provenance 3.

This research offers a review of the analytical techniques used in the rapid analysis and identification of tobacco samples of unknown provenance, comparing and identifying key differences between licit, illicit and niche tobacco not previously highlighted within one single study. The recognition of the differences between regulated large scale manufactured products and the uncontrolled cultivation of tobaccos for illicit purposes plays a significant role in the identification of trade routes, the relationship between nicotine levels and addiction, and increased adverse health effects. Each sample was subject analysis by the following methods after respective sample preparation; X-ray Fluorescence, EDX- SEM, Gas Chromatography- Mass Spectrometry, Ion Chromatography and Fourier Transform Infrared Spectroscopy. Upon analysis of results we were able to identify key discriminative features within each technique that allowed for the development of typical characteristic profiles for each type of tobacco, with the potential to efficiently replace current costly protocols within HMRC and trading standards that see tobacco analysis outsourced for identification of provenance.

References

[1] S. Verma, I. Singh, Trace metal concentrations in different Indian tobacco products and related health implications, Food and Chemical Toxicology; 48:2291-7.

[2] World Health Organization, Tobacco Smoking, IARC Monographs, 2014; 100E(6):43-170.

[3] N. L Benowitz, Nicotine Effects and Addiction, Smoking and Tobacco Control Monograph No2.

Page | 71


INVESTIGATING OXAZOLIDINE ADDUCT FORMATION FROM PSEUDOEPHEDRINE

Joel D. Smith 1, Jim Pearson 2, & Ian D. Potter 1

1 La Trobe Institute for Molecular Science, La Trobe University, Melbourne 3083, VIC, Australia

2 Victorian Police Forensics Services Department, 31 Forensic Drive, Macleod 3085, VIC, Australia

[email protected]

Oxazolidines are a class of compounds, commonly identified in clandestine mixtures associated with methamphetamine produced from pseudoephedrine [1-2]. They are believed to be formed from condensation with pseudoephedrine, and commonly encountered laboratory reagents & solvents [3-4]. It is unclear as to the specific factors that drive their formation. It is of interest to many law enforcement authorities, both in Australia and internationally to know of factors that drive their formation, and to determine whether pseudoephedrine can be recovered. The general accepted consensus is that they can form as an artefact from GCMS analysis, or unintentionally in a solution. The work reported herein, suggests that the influence of GCMS analysis is negligible, as rapid GCMS analysis revealed either a low (<1%), or no conversion. Careful monitoring of simplistic model waste systems via 1H NMR analysis showed that pseudoephedrine reacts rapidly with aldehydes to form oxazolidines, where-as oxazolidines formed from ketones occurred more slowly. These results suggest that their presence in clandestine mixtures is due to in situ formation, rather than as an artefact of GCMS analysis. Hydrolysis under acidic conditions suggests that pseudoephedrine can be recovered from its respective oxazolidine.

References

[1] Kalchik, M. Identification of Oxazolidines as a New Class of Impurities Found in Methamphetamine. J. Cland. Inv. Chem.1991, 1 (4), 17.[2] Melgoza, L. Traces of PCP Found in Methamphetamine Lab Residues. J. Cland. Inv. Chem.1997, 7 (4), 8-9.[3] McKibbin, T. They Never Learn. J. Cland. Inv. Chem.1996, 5 (4), 7.[4] Bird, C.; Della, E.; Pigou, P. The Identification of By-products in Illicit Methylamphetamine Derived from Pseudoephedrine Pharmaceuticals. J. Cland. Inv. Chem.2001, 11 (1), 11.

Page | 72


ENANTIOSELECTIVE MULTIDIMENSIONAL GAS CHROMATOGRAPHY FOR THE AUTHENTICITY CONTROL OF AUSTRALIAN M. ALTERNIFOLIA: ADULTERATION OR NATURAL VARIABILITY?

Yong Foo Wong1, Rachel N. West2, Sung-Tong Chin1, Philip J. Marriott1

1 Australian Centre for Research on Separation Science, School of Chemistry, Monash University,

Wellington Road, 3800 Victoria, Australia2 Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom

[email protected]

The potential of fast multiple heart-cut enantioselective multidimensional gas chromatography (GCeGC) and enantioselective comprehensive two-dimensional gas chromatography (eGC×GC) to perform the stereoisomeric analysis of designated chiral monoterpenes (limonene, terpinen-4-ol and α-terpineol) in Melaleuca alternifolia (tea tree oil; TTO) is demonstrated. In GCeGC, interference-free enantioresolution of individual antipodes of each optically active component was achieved using a mid-polar first dimension (1D) column and an enantioselective second dimension (2D) column. For eGC×GC study, various combinations of 1D enantioselective column and a range of 2D polar columns were evaluated. Quantification based on summation of two major modulated peak areas for each antipode was proposed, showing comparable results to that obtained in GCeGC. The suitability of using these two enantioselective multidimensional platforms for authenticity control of TTO will be evaluated and discussed. The chiral signatures for authentic Australian TTOs were established by analysing a representative number of pure TTOs sourced directly from plantation sites of known provenances throughout Australia. Principle component analysis was used to compare the obtained results with commercial TTOs sampled from different continents. The possibility of assessing these data to determine adulteration, or which have added oils that affect the enantiomeric composition, in commercially sourced TTOs will be discussed. An Australian standard that includes enantiomeric composition data for terpinen-4-ol and α–terpineol is reportedly under consideration [1].

[1] Larkman, T. Executive Director, Australian Tea Tree Industry Association (ATTIA), Pers. Commun. 2 June.2015.

Page | 73


TRANSFORMING GSR EVIDENCE – ASSESSING THE PERSISTENCE AND TRANSFERENCE OF

GUNSHOT RESIDUESNick Lucas 1, Paul Kirkbride 1, Hilton Kobus 1, and Michael Cook 2

1 Flinders University, Sturt Road, Bedford Park, 5042, SA, Australia2 Forensic Science South Australia, Divett Place, Adelaide, 5000, SA, Australia

[email protected]

Gunshot residue (GSR) is a valuable form of forensic trace evidence in the investigation of firearms crime. While a quantitative model for transfer of GSR and evaluation of the evidence has been elusive thus far[1], it is generally considered that the greater the amount of GSR detected on a suspect, the more likely the GSR originated from a firing incident, rather than from secondary transfer. However, the casework experience is often equivocal, and the potential for secondary transfer – including transfer from police in the process of arrest – may affect the significance of results. To ensure a GSR test result is given appropriate weighting in court, the dynamics of the deposition, retention and distribution of GSR in the aftermath of a firing event must be clearly understood.

The retention of GSR on a subject is significantly influenced the activity of the subject after firing [2]. Cases of suicide involving a firearm provide an opportunity to assess GSR distribution and retention, assuming no movement of the shooter after firing. Seventy-one cases of suicide by gunshot in South Australia between 1998 and 2014 were examined to collect data on firearm type, calibre, and gunshot residue test results. Overall, 47% of cases were found to produce GSR results of little probative value, even though it was known that the shooter had fired a firearm. Of particular interest were cases involving 0.22 rim fire ammunition, for which characteristic particles are not expected due to lack of antimony present in the primer[3]. Despite this, 64% of these cases resulted in the detection of antimony-containing, three component particles, indicating that significant numbers of three component particles may be present in cases where they were previously unexpected. Despite the lack of activity by the subject, GSR particle recovery was still seen to fall significantly with time.

References

[1] Gauriot R, Gunaratnam L, Moroni R, Reinikainen T, Corander J. Statistical challenges in the quantification of gunshot residue evidence. Journal of forensic sciences. 2013;58:1149-55.[2] Kilty JW. Activity after shooting and its effect on the retention of primer residue. J Forensic Sci. 1975;20:219-30.[3] Wrobel HA, Millar JJ, Kijek M. Identification of ammunition from gunshot residues and other cartridge related materials-A preliminary model using. 22 caliber rimfire ammunition. Journal of forensic sciences. 1998;43:324-8.

Page | 74


IMPACTS OF ARSENIC AND ANTIMONY LABILITY FROM RECENTLY AND HISTORICALLY

CONTAMINATED SOILS AND ITS EFFECTS ON WATER SPINACH (Ipomoea aquatic)

Lakmini P. Egodawatta 1 , Gabriella Macoustra2, Lien Ngo3 and Dianne F. Jolley4

School of Chemistry, University of Wollongong, 2522, NSW, Australia

[email protected]

As and Sb enter the environment from industrial process, use of flame retardants, ammunition use and pesticides. Their ultimate fate is in soils and sediment. There is increasing evidence of elevated concentrations of As and Sb in agricultural soils[1]. The kinetics of As in waters and soils has been extensively studied, however the Sb toxicity mechanism on plants and its’ bioavailability remain unknown. As and Sb have been assumed to behave the same due to their similar chemistries, but recent studies have suggested that this may not be the case.

The bioavailability of As and Sb in soils is affected by the soil characteristics, metal species and inorganic/organic ligands such as low molecular weight organic acids (LMWOA), humic and fulvic acids, phosphates, sulfates) [2]. The processes including surface precipitation/ oxidation, cavity entrapment, diffusion into microspores or incorporation into crystal lattices [3] which depend on time are also important parameters influencing As and Sb mobility in soils.

This research has investigated the phytotoxicity of As and Sb on the water spinach (Ipomoea aquatic) in soils (both historically contaminated and recently spiked) by using root and shoot growth (biomass and length), tissue accumulation and photosynthetic efficiency. The lability of As and Sb was determined by soil Sequential Extraction Procedure and compared to total extractable soil concentrations and tissue bioaccumulation. In aged soils labile-Sb was more toxic to the I. aquatic sensitivity, whereas in the spiked soils As was more toxic. Results showed that tissue mass in spiked soil was inhibited at total concentrations > 400 mg (As)/kg and > 1200 mg(Sb)/kg and bioavailable concentrations > 164 mg (As)/kg and > 800 mg(Sb)/kg. The results also suggest that plant exposure to historically contaminated aged soils have more toxic effect on plant growth than spiked soils.

References

[1] Pierart, A.;Shahid, M.;Delmas, N. S.; Dumat, C. Antimony bioavailability: knowledge and research persepectives for sustainable agricultures Journal of Hazardous Materials 289 (2015) 219 -234.

[2] Komarek, M.; Vanek, A.; Ettler, V. Chemical stabilization of metals and arsenic in contaminated soils using oxides-A review Environmental pollution 2013, 172, 9-22.

[3] Wang, Y.; Zeng, X.; Lu, Y; Su, S.; Bai, L.; Li, L; Wu, C.; Effect of aging on the bioavailability and fractionation of arsenic in soils derived from five parent materials in a red soil region of southern China Environmental pollution 2015, 207,79-87.

Page | 75


MINIATURISED MEDIUM PRESSURE CAPILLARY LIQUID CHROMATOGRAPHY SYSTEM WITH

FLEXIBLE OPEN PLATFORM DESIGN USING OFF-THE-SHELF MICROFLUIDIC COMPONENTS

Yan Li1, Miloš Dvořák1,2, Pavel N. Nesterenko1, Roger Stanley3, Mirek Macka1

1. School of Physical Sciences and Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75, Hobart 7001, Australia,

[email protected]. Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno

University of Technology, Brno, Czech Republic3. Centre for Food Innovation, University of Tasmania, Locked Bag 1370, Launceston

7250, Australia*[email protected]

In contrast to the trends of the last decades towards miniaturised and portable instrumentation to be used outside of the laboratory (on-site, in-filed), portable LC instrumentation that can be used for rapid on-site analyses has not progressed towards routine applications. In previous studies on portable LC, most of the designs relied strongly on in-house fabricated components, thus significantly limiting the availability of such portable systems for other users. A miniaturised medium pressure capillary LC (MPLC) system with gradient elution capability has been designed based on a flexible modular microfluidic system using primarily off-the-shelf low cost components to ensure wide accessibility to other analysts. The basis of the system is a modular microfluidic platform with the components assembled in a flexible manner on a breadboard. The backbone of the system was a breadboard assembled modular flexible microfluidic system (LabSmith), complemented with other off-the-shelf components, including an injection valve and on-capillary detectors, all operated through a PC. The portable LC system can accommodate six syringe pumps with 100, 20 and 5 µL syringe options, and maximum backpressures of up to 11.4 ± 0.4 MPa (water) for the 5 µL syringe, with two syringes used for each A and B mobile phase in gradient operation and another pump for sampling and one in reserve for post-column derivatisation. Sample was injected by a nano LC sampling valve, directly connected to a Chromolith CapRod RP-18 monolithic capillary column. On capillary LED based UV vis photometric detection was conducted through a piece of equal diameter PTFE-coated fused silica capillary connected after the column. The performance of the portable LC system was evaluated theoretically and experimentally, including the maximum operating pressure, gradient mixing performance, and the separation performance. Test analytes of charged and uncharged dyes and pharmaceuticals of varying hydrophobicity.

References:

[1] Li, Y.; Dvořák, M.; Nesterenko, P. N.; Stanley, R.; Nuchtavorn, N.; Krčmová, L. K.; Aufartová, J.; Macka, M., Miniaturised medium pressure capillary liquid chromatography system with flexible open platform design using off-the-shelf microfluidic components. Accepted 4 September 2015, In press. Anal. Chim. Acta.

Page | 76


TOWARDS MICROFLUIDIC FLOW CELLS FOR CHEMILUMINESCENCE DETECTION

Kara B. Spilstead 1, 2, Paul S. Francis 1, Neil W. Barnett 1, Stephen J. Haswell 2

1 Deakin University, Geelong, Australia. School of Life and Environmental Sciences, Centre for Chemistry and Biotechnology, (Waurn Ponds Campus). 75 Pigdons Road. Locked Bag

20000, Geelong, VIC 3220, Australia2 Deakin University, Geelong, Australia. School of Life and Environmental Sciences, Centre

for Regional and Rural Futures, (Waurn Ponds Campus). 75 Pigdons Road. Locked Bag 20000, Geelong, VIC 3220, Australia

[email protected]

Flow cells used in Flow Injection Analysis (FIA) for chemiluminescence detection have developed over the years, from simple coiled tubing [1] to machined complex serpentine designs [2], with optimised channel dimensions for maximum signal intensity [3]. With microfluidic technologies becoming a greater part of analytical chemistry, there is a need to explore ways in which to maximise the signal from the chemiluminescence reactions within microfluidic-sized channels. Stieg and Nieman investigated the effect of white versus black reaction chambers on chemiluminescence signal intensities in 1978 [4], but no further research has been conducted on the effect of other coloured materials on signal intensities. This work entails studies on microfluidic sized channels (0.4mm × 0.2mm) milled into different coloured acrylics, with FIA and photographic analysis of the chemiluminescence intensities to determine the effect of these coloured materials, and their potential application in microfluidic devices.

References:

[1] Burguera, J. L.; Townshend, A., Flow injection techniques. Monitoring chemiluminescent reactions by flow injection analysis. Proceedings of the Analytical Division of the Chemical Society 1979, 16 (9), 262-264.[2] Terry, J. M.; Adcock, J. L.; Olson, D. C.; Wolcott, D. K.; Schwanger, C.; Hill, L. A.; Barnett, N. W.; Francis, P. S., Chemiluminescence Detector with a Serpentine Flow Cell. Analytical Chemistry 2008, 80 (24), 9817-9821.[3] Mohr, S.; Terry, J. M.; Adcock, J. L.; Fielden, P. R.; Goddard, N. J.; Barnett, N. W.; Wolcott, D. K.; Francis, P. S., Precision milled flow-cells for chemiluminescence detection. Analyst 2009, 134 (11), 2233-2238.[4] Stieg, S.; Nieman, T. A., Experimental and theoretical considerations of flow cell design in analytical chemiluminescence. Analytical Chemistry 1978, 50 (3), 401-404.

Page | 77


A MULTI-RESIDUE DRIED BLOOD SPOT METHOD FOR DOPING CONTROL USING AN ALTERNATIVE

BLOOD COLLECTION PLATFORMChristopher Tangvisethpat 1,2, Janelle Grainger 1, Catrin Goebel 1, Adrian V.

George 2

1 Australian Sports Drug Testing Laboratory, National Measurement Institute, 105 Delhi Road, North Ryde 2113, NSW, Australia

2 School of Chemistry, The University of Sydney 2006, NSW, Australia

[email protected]

Doping control is an ongoing problem for sports regulatory bodies and the wider community [1]. Dried blood spots (DBS) are currently used in neonatal and pharmaceutical screening [2]. They are a desirable matrix for doping control due to their low sampling volume and sample stability [2,3]. DBS are traditionally sampled onto filter paper, however sampling inconsistency can result from factors such as blood viscosity [4]. A multi-residue DBS drug screening method was developed and validated for an alternative sampling platform that attempts to address the limitations of filter paper media. Over 200 substances across 8 different classes of drugs prohibited by the World Anti-Doping Agency (WADA) were included in the assay. This method was developed for ultra-high performance liquid chromatography high resolution mass spectrometry. Method validation demonstrated that the method was fit for screening purposes for the majority of analytes. Linear conditions and high specificity were achieved for the majority of substances, mostly with limits of detection below 25% of the laboratory performance levels mandated by WADA. Acceptable precision (<30% relative standard deviation) was achieved for most analytes, for instrument precision, repeatability, recovery, and robustness. Simple excretion studies were also performed where three over-the-counter drugs were successfully extracted and detected in physiological conditions.

References:

[1] World Anti-Doping Agency, 2013 Anti-Doping Testing Figures: Laboratory Report. https://wada-main-prod.s3.amazonaws.com/resources/files/WADA-2013-Anti-Doping-Testing-Figures-LABORATORY-REPORT.pdf (accessed 5 August 2014).

[2] Sharma, A.; Jaiswal, S.; Shukla, M.; Lal, J., Dried blood spots: Concepts, present status, and future perspectives in bioanalysis. Drug Test. Anal. 2014, 6 (5), 399-414.

[3] Tretzel, L.; Thomas, A.; Geyer, H.; Gmeiner, G.; Forsdahl, G.; Pop, V.; Schänzer, W.; Thevis, M., Use of dried blood spots in doping control analysis of anabolic steroid esters. J. Pharm. Biomed. Anal. 2014, 96, 21-30.

[4] O'Mara, M.; Hudson-Curtis, B.; Olson, K.; Yueh, Y.; Dunn, J.; Spooner, N., The effect of hematocrit and punch location on assay bias during quantitative bioanalysis of dried blood spot samples. Bioanalysis 2011, 3 (20), 2335-2347.

Page | 78


INVESTIGATIONS INTO THE PHYSICAL PROPERTIES OF LATENT FINGERMARKS USING

ATOMIC FORCE MICROSCOPY Buddhika N. Dorakumbura 1,2, Thomas Becker 1,2, and Simon W. Lewis 1,2

1 Nanochemistry Research Institute, GPO Box U1987, Perth, Western Australia, Australia2 Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia,

Australia

[email protected]

While there are numerous techniques for detecting latent fingermarks, which exploit the physical or chemical properties of the fingermark deposit, only a limited number of them are fully understood [1]. It is suggested that the lack of fundamental knowledge about the physical properties of the latent fingermark deposit itself greatly hampers any efforts in understanding the underlying mechanisms, the development of novel techniques or the improvement of existing ones [2]. Here we present an approach to explore the physical properties of latent fingermarks, such as topography and adhesion, and their ageing over time through the use of atomic force microscopy (AFM). PeakForce Quantum Nanomechanics (PF QNM) is a novel imaging mode in AFM which allows simultaneous acquisition of high-resolution topography images and localised measurements of nanomechanical sample properties at a very high speed [3].

Variations in the topography and adhesion of latent fingermark droplets have been investigated over a period of four weeks using PF QNM. The results show that this technique is effective in resolving nano-scale features of fingermark samples. Observed differences in the distribution of chemical components within an individual droplet suggest that a fingermark droplet itself is a mixture of compounds with different hydrophilicities. The changes in topography and adhesion of eccrine sweat rich deposits as they age were successfully demonstrated, which was challenging with other techniques due to the small amount of secretions present [2]. Moreover, significant changes in the adhesiveness of normal fingermark droplets were observed during the 4 weeks following fingermark deposition.

References

1. Champod C., L. C., Margot P., Stoilovic M., Fingerprint Detection Techniques. In Fingerprints and Other Ridge Skin Impressions, CRC Press: 2004.

2. Moret, S.; Spindler, X.; Lennard, C.; Roux, C., Microscopic examination of fingermark residues: Opportunities for fundamental studies. Forensic Science International 2015.

3. B. Pittenger, N. E., C. Su Quantitative Mechanical Property Mapping at the Nanoscale with PeakForce QNM; Bruker Corporation: 2012.

Page | 79


THE TOXICITY OF ALUMINIUM TO MARINE DIATOMS

Megan L. Gillmore 1,2, Lisa A. Golding1, Brad M. Angel1, Merrin S. Adams1, Dianne F. Jolley2

1 CSIRO Land and Water, Lucas Heights, 2234, NSW, Australia2 University of Wollongong, Wollongong, 2522, NSW, Australia

[email protected]

Over the past few decades, localised inputs of aluminium to the marine environment have increased as a consequence of anthropogenic activities, such as coastal mining and dredging operations, discharges associated with alumina production, and the disturbance or drainage of acid sulfate soils for coastal development. These inputs have led to high concentrations of aluminium being measured in industrial harbours and coastal waters, which have the potential for adverse effects on aquatic organisms. This research investigated the toxicity of 72-h exposures of aluminium to three marine diatoms (Ceratoneis closterium (formerly Nitzschia closterium), Minutocellus polymorphus and Phaeodactylum tricornutum) by measuring population growth rate inhibition and cell membrane damage (SYTOX Green) as endpoints. Toxicity was correlated to the time-averaged concentrations of different aluminium size-fractions, operationally defined as <0.025 µm, <0.45 µm filtered (dissolved) and unfiltered (total) present in solution over the 72-h bioassay. The chronic population growth rate inhibition after aluminium exposure varied between diatom species. C. closterium was the most sensitive species (10% inhibition of growth rate (72-h IC10) of 80 (55–100) µg Al/L (95% confidence limits)) while M. polymorphus (540 (460–600) µg Al/L) and P. tricornutum (2100 (2000–2200) µg Al/L) were less sensitive (based on measured total aluminium). Dissolved aluminium was the primary contributor to toxicity in C. closterium, while a combination of dissolved and precipitated aluminium forms contributed to toxicity in M. polymorphus. In contrast, aluminium toxicity to the most tolerant diatom P. tricornutum was due predominantly to precipitated aluminium. No effects on plasma membrane permeability were observed for any of the three diatoms suggesting that mechanisms of aluminium toxicity to diatoms do not involve compromising the plasma membrane. These results indicate that marine diatoms have a broad range in sensitivity to aluminium with toxic mechanisms related to both dissolved and precipitated aluminium.

Page | 80


Page | 81


Oral AbstractsTuesday 8th December

Page | 82


AN AUTOMATED CHROMATOGRAPHY PROCEDURE OPTIMIZED FOR STABLE Cu

ISOTOPE SEPARATION FROM BIOLOGICAL SOURCE MATERIALS

T. Gabriel Enge1, M. Paul Field2, Dianne F. Jolley3, Heath Ecroyd4, M. Hwan

Kim2 and Anthony Dosseto1

1 University of Wollongong, School of Earth and Environmental Sciences, 2522, NSW, Australia

2 Elemental Scientific Inc., 7277 World Communications Drive, NE 68122, USA3 University of Wollongong, School of Chemistry, 2522, NSW, Australia

4 University of Wollongong, Illawarra Health and Medical Research Institute, 2522, NSW, Australia

[email protected]

An automated ion exchange chromatography method was developed for the separation of Cu from biological samples prior to stable, naturally-occurring isotope analysis. In contrast to previous methods [1,2], the technique does not require for the Cu to be fully oxidized/reduced into either Cu+ or Cu2+. Distribution coefficients of Cu and other cations to the Cu-specific anion exchange resin applied here, are pH dependant rather than the oxidation state of the Cu. This enables the effective purification and separation of Cu from complex matrixes using a single, reusable chromatographic column. The method is adjustable to varying sample types and enables high sample throughput, with the system being able of unattended processing of up to 60 samples per run at a rate of 36 samples/day on a single column. Low carryover combined with high yields for multiple extractions were observed, ensuring high purity of the Cu separates. Method validation confirmed that the procedure yields appropriately pure Cu fractions after a single column pass, with a recovery of 97±3%. Isotopic analyses of the Cu fraction by multi-collector inductively-coupled plasma mass spectrometry, produced accurate Cu stable isotope data. The reproducibility was assessed as <0.01‰ for pure standard solutions and ±0.01‰ for samples of biological origin, making this method suitable for future applications that require high throughput, as well as very good reproducibility e.g. medical research.

References:

[1] Larner, F.; Rehkämper, M.; Coles, B. J.; Kreissig, K.; Weiss, D. J.; Sampson, B.; Unsworth, C.; Strekopytov, S. J. Anal. At. Spectrom. 2011, 26 (8), 1627.

[2] Maréchal, C. N.; Télouk, P.; Albarède, F. Chem. Geol. 1999, 156 (1-4), 251.

Page | 83


APPLICATION OF MULTIDIMENSIONAL GAS CHROMATOGRAPHY TO ASSESS THE EFFECTIVENESS OF RE-ADDITION OF ANTIOXIDANT TO AGED JET FUELS

Renée L. Webster 1,2, Christy-Anne Stansfield 2, David J. Evans2, Paul M. Rawson2,3, Philip J. Marriott1

1 Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Clayton 3800, VIC, Australia

2 Aerospace Division, Defence Science and Technology Group, 506 Lorimer St, Fishermans Bend, 3207, VIC, Australia

1 School of Aerospace, Mechanical and Manufacturing Engineering, RMIT University, 124a Latrobe Street, Melbourne,3000, VIC, Australia

[email protected]

Long term storage of aviation turbine fuels often requires the use of antioxidants with many military fuel specifications mandating its addition for hydroprocessed fuels1. Different fuel refinery processing methods are known to affect the storage stability of fuels where unstabilised fuels react with oxygen to form hydroperoxides. These hydroperoxide species initiate autoxidation reactions ultimately forming sediments and gums which lead to increased maintenance, poor performance and engine failures2. This work examines the influence of antioxidants on aged and freshly refined aviation turbine fuels of various types, some containing antioxidant at manufacture and others not. Antioxidants were analysed using heart-cutting gas chromatography mass spectrometry (GC-MS) to assist in deconvolving the complex chromatogram and clearly demonstrates the difficulties encountered in quantifying antioxidant compounds even using high resolution separations. The rate of antioxidant depletion is reported along with the re-stabilised fuel’s oxidation stability measurement. It was found that some fuel types do not benefit from re-addition of antioxidant and no improvement was observed for inhibition of hydroperoxide formation in aged fuels, however oxidation induction times were improved for re-addition of antioxidant for all fuels examined3.

References

[1] Military Specification MIL-DTL-83133H, Detail Specification Turbine Fuel, Aviation, Kerosene Type, JP-8 (NATO F-34), NATO F-35, and JP-8+100 (NATO F-37), Department of Defense 2011. [2] Heneghan, S. P.; Zabarnick, S., Oxidation of Jet Fuels and the Formation of Deposit. Fuel 1994, 73, (1), 35-43. [3] Rawson, P. M.; Stansfield, C.-A.; Webster, R. L.; Evans, D., Re-addition of antioxidant to aged MEROX and hydroprocessed jet fuels. Fuel 2015, 139, (1), 652-658.

Page | 84


FABRICATION AND EVALUATION OF POLY (DIMETHYLSILOXANE)-DIAMOND ELECTROPHORETIC

CHIPSidra Waheed 1,2, Joan M. Cabot 1,2, Niall P Macdonald1,2

, Trevor Lewis 1, Michael Breadmore 1,2, Brett Paull 1,2

1ARC Centre of Excellence for Electromaterials Science (ACES), School of Chemistry, University of Tasmania, Hobart, 7001, TAS, Australia

2Australian Centre for research on separation sciences (Across), School of Chemistry, University of Tasmania, Hobart, 7001, TAS, Australia

[email protected]

Miniaturisation of electrophoretic analytical devices is a continuously growing field; such devices are not only portable but they also offer rapid analysis with reduced reagent consumption [1]. Since the beginning of 1990’s the choice of material for miniaturised electrophoretic devices has shifted away from the traditional materials towards polymers. The distinct advantage of using polymers is the fact they are inexpensive, mechanically robust, disposable and amenable to modification. Apart from all the above advantages, unfortunately polymeric materials exhibit inherently low thermal conductivities, which retard the dissipation of internally generated heat (commonly referred as Joule heating) during electrophoresis [2]. Joule heating is an important phenomenon in electro-driven separations as it induces temperature changes in the electrolyte and thereby detrimental influences on precision, accuracy, separation efficiency and method robustness [3].

In order to overcome limitation of joule heating effect within a polymeric electrophoretic chip, we try to exploit properties of diamonds. Its inertness, optical transparency and high thermal conductivity make it suitable for incorporation within polydimethylsiloxane (PDMS) [4]. We fabricated a composite electrophoretic chip via soft lithography (also known as replica method) [5]; this method involves fabrication of a SU-8 master mould that served as a template. The PDMS chip containing diamond was cast with this mould and baked in an oven. Chip morphology, surface roughness and channels dimensions were examined for all composites and electroosmotic flow was then studied. Overall, this presentation elucidates the effect of diamond on heat dissipation for improved separation efficacy in biological and environmental applications.

References:

[1] Harrison, D. J.; Manz, A.; Fan,Z.; Leudi, H.; Widmer, H. M. Capillary Electrophoresis and Sample Injection Systems Integrated on a Planar Glass Chip. Anal. Chem. 1992, 64, 1926-1932.[2] Erickson, D.; Sinton, D; Li, D. Joule Heating and Heat Transfer in Poly (dimethylsiloxane) Microfluidic Systems. Lab Chip 2003, 3, 141-149.[3] Evenhuis, J. C.; Guigt, M. R.; Macka, M.; Marriott, J. P.; Haddad, R.P. Temperature profiles and Heat Dissipation in Capillary Electrophoresis. Anal. Chem. 2006, 78, 2684-2693.[4] Khanna, P.; Villagra, A.; Kim,S.; Seto,E.; Jaroszeski,M,; Kumar, A.; Bhansali, S. Use of Nanocrystalline Diamond for Microfluidic Lab-on-a-chip. Diamond Relat. Mater. 2006, 15, 2073-2077. [5] Xia, Y.; Whitesides, M. G. Soft Lithography. Angew. Chem. Int. Ed. 1998, 37, 550 -575

Page | 85


SELECTIVE DETECTION OF SYNTHETIC CANNABINOIDS.

Niki K. Burns 1, Paul G. Stevenson1, James R. Pearson2, Xavier A. Conlan 1

1 Centre for Chemistry and Biotechnology Deakin University, Pigdons Road Geelong, Victoria, 3217

2 Victoria Police Forensic Services Department, Macleod, Victoria, 3085

[email protected]

In Victoria, synthetic cannabinoids have recently been made illegal under an amendment to the drugs, poisons and controlled substances act 1981. Identification of synthetic cannabinoids in popular brands of ‘incense’ and ‘potpourri’ has been a difficult and challenging task due to the sample complexity and changes observed in the chemical composition of the cannabinoids of interest.

This study has developed analytical methodology for the targeted extraction and determination of synthetic cannabinoids available pre-ban. A simple solvent extraction was developed using acetonitrile that extracted the cannabinoid of interest off the herbal substrate. High performance liquid chromatography coupled with UV‐visible and chemiluminescence detection (acidic potassium permanganate, manganese IV and tris (2,2‐bipyridine) ruthenium(III)) were used to interrogate the synthetic cannabinoid products. The tris(2,2‐bipyridine)ruthenium(III) detection was found to offer better sensitivity than the permanganate based reagents. In twelve different brands of herbal incense, cannabinoids were extracted and identified including UR‐144, XLR 11, AM2201, 5‐F‐AKB48 and A796‐260. Six standards were quantitatively analysed to obtain the concentration of synthetic cannabinoids within the herbal blends, and also to find the limits of detection.

Page | 86


THE NATURE OF THE SALT ERROR IN THE Sn(II)-REDUCED MOLYBDENUM BLUE REACTION FOR

DETERMINATION OF DISSOLVED REACTIVE PHOSPHORUS IN SALINE WATERS

Edward A. Nagul 1,2, Ian D. McKelvie1,3, Spas D. Kolev 1,2

1 School of Chemistry, The University of Melbourne, 3010, VIC, Australia2Centre for Aquatic Pollution Identification and Management (CAPIM), The University of

Melbourne, 3010, VIC, Australia3School of Geography, Earth and Environmental Sciences, Plymouth University, Plymouth

PL48AA, UK

[email protected]

Sn(II) is a well-known reductant used in molybdenum blue (MB) methods for the determination of dissolved reactive phosphorus (DRP) in waters because it rapidly and quantitatively performs the reduction step which generates a coloured product. However, in saline waters, this method suffers from a salt error which causes a significant decrease in sensitivity, and this phenomenon has never been adequately explained in the literature. The Murphy and Riley method, which uses Sb(III) and ascorbic acid for the reduction step, is preferred for DRP determination in saline waters because it is unaffected by salinity, but it exhibits a sensitivity approximately 30% lower than that when Sn(II) is used as the reductant without Cl- interference. This study [1] investigates the processes causing the salt error and possible ways of minimizing it, so that the benefits of Sn(II) reduction on the molybdenum blue reaction rate and sensitivity may be exploited in the determination of low levels of DRP in marine and estuarine waters. It has been established that the salt error is caused by the formation of Sn(IV) chloro-complexes which compete with the formation of Sn(IV)-substituted phosphomolybdenum blue, forcing the reaction to proceed via the much slower, less favourable process of direct reduction that occurs in methods using organic reductants such as ascorbic acid.

Reference:

[1] Nagul, E. A.; McKelvie, I. D.; Kolev, S. D., The nature of the salt error in the Sn(II)-reduced molybdenum blue reaction for determination of dissolved reactive phosphorus in saline waters. Anal. Chim. Acta 896 2015, 120-127.

Page | 87


STABILITY AND SELECTIVITY OF POLYMER INCLUSION MEMBRANE (PIMs) CONTAINING

DINONYLNAPHTHALENE SULFONIC ACIDMandana Ershad 1, M. Ines G. S. Almeida 1, Robert W. Cattrall 1, Spas D.

Kolev 1

1 School of Chemistry, The University of Melbourne, 3010, VIC, Australia

[email protected]

Polymer Inclusion Membranes (PIMs) are polymer-based liquid membranes, capable of both extraction and back-extraction of ionic species in a single step, requiring little consumption of usually expensive extractants and toxic organic diluents. Therefore, they are viewed as a promising and greener alternative to traditional solvent extraction [1]. PIMs are usually composed of an extractant (carrier), a base polymer and a plasticizer or modifier (if necessary), and they generally demonstrate superior stability in comparison with other liquid membranes (e.g. supported liquid membranes).

The extractant is responsible for binding with the species of interest and transporting it across the PIM. In this study dinonylnaphthalene sulfonic acid (DNNS), a commercially available acidic carrier, has been chosen due to its cationic-exchange properties and high selectivity towards ions of environmental interest (e.g. ammonium, zinc). This extractant is normally supplied as a 50% solution in 2-butoxy ethanol, which is soluble in water. As a result, the stability of DNNS-based PIMs is likely to be compromised. Therefore, it can be expected membrane stability can be improved if commercial DNNS is purified before use in order to eliminate 2-butoxyethanol. Hence, the aim of the present work consists of a comparison study of the stability of PIMs prepared with commercial and purified DNNS, using ammonium as a model analyte. The preparation of stable DNNS-based PIMs will then allow the determination of their selectivity towards a wide range of chemical species of environmental concern. Gas chromatography was used to characterize the solvent composition of DNNS and confirm the absence of 2-butoxy ethanol in the purified DNNS. PIMs composed of 35% wt. commercial/purified DNNS as carrier, 10% wt. 1-tetradecanol as modifier and 55% wt. poly(vinylchloride) as base polymer [2] were characterized by thermogravimetric analysis. These membranes were also used in extraction experiments using 3.0 mg NH4

+ L-1 as source solution and purified DNNS-based PIMs showed to be significantly more stable than commercial DNNS-based membranes.

References:[1] Almeida M.I.G.S.; Silva A.M.L.; Cattrall R.W.; Kolev S.D. Recent trends in extraction and transport of metal ions using Polymer Inclusion Membranes (PIMs) J. Membr. Sci, 415 2012, 9-23[2] Almeida M.I.G.S.; Cattrall R.W.; Kolev S.D. A study of ammonium ion extraction properties of polymer inclusion membranes containing commercial dinonylnaphthalene sulfonic acid. J. Membr. Sci, 2015, 155-162

Page | 88


LOW-CONCENTRATION AMMONIA GAS DETECTION ON MINIATURISED ELECTRODES IN

ROOM TEMPERATURE IONIC LIQUIDSGhulam Hussain 1, Debbie S. Silvester 1

1 Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth WA 6845, Australia

[email protected]

The detection of low concentrations of ammonia (NH3) gas is of huge importance due to its use in a wide range of industries and its high toxicity. Concentrations as low as 500 ppm can be lethal, and the current (USA) Occupational Health and Safety Permissible Exposure Limit (OSHA PEL) is 25 ppm in the gas phase. Amperometric gas sensors (AGSs) for ammonia are commercially available, however they typically employ water/sulphuric acid electrolytes, and their lifetimes are limited by how quickly the solvent dries up. Room Temperature Ionic Liquids (RTILs) have been attracting attention [1] as replacement solvents in AGSs due to their favourable physical properties such as high intrinsic conductivity, wide electrochemical windows, low volatility, high chemical and thermal stability and the ability to solubilise a range of compounds. Importantly, they do not evaporate when exposed to high gas flow, and can function in hot and dry environments. In our work, we are investigating new commercially available thin-film electrode surfaces, consisting of 3 electrodes printed onto a small area on an inert substrate. The small size means that only a few microliters of RTIL solvent are needed, and the small amount of inert metal (e.g. platinum) required, minimises the overall cost of the sensor. A comparison of different voltametric techniques will be provided for ammonia oxidation: linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV), over the concentration range of 10-100 ppm NH3. The results on commercially available Pt thin-film electrodes, microarray thin-film electrodes, and screen-printed electrodes will be compared to “ideal” Pt microdisk electrodes. Calibration curves (current vs. concentration) for all voltametric techniques on all 4 surfaces will be presented, showing excellent linearity and limits of detection in the range of ca. 2-5 ppm, much lower than the 25 ppm exposure limit for NH3. These results are highly encouraging and suggest that RTILs and low-cost miniaturised electrodes can be combined in sensor devices to detect ammonia gas at low concentrations.

References:

[1] Buzzeo, M. C.; Hardacre, C.; Compton, R. G. Use of Room Temperature Ionic Liquids in Gas Sensor Design. Anal Chem. 2004, 76, 4583-4588.

Page | 89


SOLID-PHASE MICROEXTRACTION LOW TEMPERATURE PLASMA MASS SPECTROMETRY

FOR THE DIRECT AND RAPID ANALYSIS OF CHEMICAL WARFARE SIMULANTS IN COMPLEX

MIXTURESMorphy C. Dumlao, J. Justin Gooding, William A. Donald

School of Chemistry, University of New South Wales, Sydney, New South Wales, 2052, Australia

[email protected]

An important goal is to develop a portable ionization source for mass spectrometry that is ultrasensitive and highly tolerant of complex mixtures. Here, we report the direct integration of solid-phase microextraction (SPME) with a low temperature plasma ion source[1] to rapidly detect chemical warfare agent (CWA) simulants and their hydrolysis products in complex mixtures, including urine. In this sampling and ionization method, the fiber serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME probe electrode. By fabricating a stainless steel probe coated with a Linde Type A (LTA) zeolitic microporous material, a 5000-fold and 200-fold enhancement in the detected ion abundances were obtained for detecting organophosphates in spiked water and urine samples, respectively, compared to uncoated SPME probes. The LTA limits of detection (LODs) for each CWA simulants and hydrolysis products were lower than the required limits for Organization for the Prohibition of Chemical Weapon (OPCW) proficiency testing (< 10 ppm). The use of the LTA coating significantly outperformed the use of high alumina ZSM-5 zeolite coating of comparable thickness that is significantly more hydrophobic than LTA. The sampling and detection of CWA analogues and hydrolysis products required less than 2 min. A key advantage of this sampling and ionization technique is that analyte ions can be directly and rapidly sampled from complex mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove highly beneficial for portable mass spectrometry [2] applications because high performance can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the ion source is compact, can be readily powered with a 9V DC battery, and is highly tolerant of complex mixtures.

References:

[1] Stephens, E. R.; Dumlao, M.; Xiao, D.; Zhang, D.; Donald, W. A., Benzylammonium Thermometer Ions: Internal Energies of Ions Formed by Low Temperature Plasma and Atmospheric Pressure Chemical Ionization. J. Am. Soc. Mass Spectrom. 2015, DOI: 10.1007/s13361-015-1272-1. [2] Dumlao, M.; Sinues, P. M.-L.; Nudnova, M.; Zenobi, R., Real-time detection of chemical warfare agent simulants in forensic samples using active capillary plasma ionization with benchtop and field-deployable mass spectrometers. Anal. Methods 2014, 6 (11), 3604-3609.

Page | 90


AN ALTERNATIVE SAMPLE PREPARATION METHOD FOR THE DETECTION OF DRUGS IN HAIR

Caitlyn A. Rogers1, Michaela Kenneally2, Peter C. Stockham1,2, Claire E. Lenehan1, Paul Kirkbride1

1 Flinders University, School of Chemical & Physical Sciences, Sturt Rd, Bedford Park 5042 SA, Australia

2 Forensic Science SA, Toxicology, 21 Divett Place, Adelaide 5000 SA, Australia

[email protected]

The analysis of drugs from hair samples can provide forensic toxicologists a great deal of information that cannot be gained through the analysis of blood and urine. Hair analysis is usually performed as a complementary technique to blood and urine analysis, but has the added advantages of having a greater detection window (months to years, compared to hours to days). This longer detection window allows for determination of chronic drug use, chronic poisoning, the monitoring of drug abstinence and obtaining a drug history. Despite the added advantages, there are no recognised standard methods for hair analysis which is a particular concern as a variety of solvents and incubation conditions can be used, differing widely from lab to lab. Another issue with hair analysis is the length of incubation (usually between 8-24hours) required for sample preparation. This aspect is very time consuming which can be a hindrance on the overall analysis process. This research introduces a fast method of extraction which involves the use of microwave irradiation and an ionic liquid composite, in place of the standard solvent incubation, to disassemble the structure of the hair, releasing the target analytes. This vastly reduces the time required for sample extraction from hours to minutes.

Page | 91


Oral AbstractsWednesday 9th December

Page | 92


SPECTROSCOPIC CHARACTERISATION OF AUTOMOTIVE WINDOW TINT FOR FORENSIC

PURPOSESKarin J. van der Pal 12, Santusha Pandra 1, Mark Maric ‡

12, Wilhelm van Bronswijk 1

and Simon W. Lewis 12 a Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia,

6845b Nanochemistry Research Institute, GPO Box U1987, Perth, Western Australia, 6845

‡Current address: National Centre of Forensic Science, University of Central Florida, PO Box 162367, Orlando, Florida USA 32816

[email protected]

Due to the prevalence of polymers in everyday products, polymeric trace evidence is an important aspect of forensic science in respect to its ability to provide associations between people, objects and places; and this is no exception in regards to crime or accidents involving motor vehicles [1-4]. One form of potential trace evidence from such incidents is automotive window tint.

Automotive window tint samples were analysed using transmission ultraviolet-visible spectroscopy [5]. The spectra showed features characteristic of known window tint film components such as polyethylene terephthalate and cyclic imino esters. Principal component analysis showed that samples cluster by both groups of supplier and individual samples, indicating good reproducibility and sample separation. Window tint samples could be traced back to one of three countries of manufacture; Australia, USA and Israel; suggesting that suppliers are sourcing their samples from the same manufacturer. This indicates the potential for window tint to be used as forensic evidence, as samples are able to be compared on a questioned versus known basis due to the variation in the sources. It also opens up the potential for reducing the number of possible vehicles of interest when only a questioned sample is available.

1. White, P., Crime scene to court: the essentials of forensic science. 2010: Royal society of chemistry.2. Houck, M.M. and J.A. Siegel, Fundamentals of Forensic Science. 2 ed. 2010, China: Elsevier Academic Press.3. Causin, V., Polymers on the crime scene: How can analytical chemistry help to exploit the information from these

mute witnesses? Analytical Methods, 2010. 2(7): p. 792-804.4. Causin, V., et al., The Discrimination Potential of Ultraviolet-Visible Spectrophotometry, Thin Layer Chromatography,

and Fourier Transform Infrared Spectroscopy for the Forensic Analysis of Black and Blue Ballpoint Inks. J. Forensic Sci., 2008. 53(6): p. 1468-1473.

5. van der Pal, K.J., et al., Ultraviolet-visible spectroscopic characterisation of automotive window tints for forensic purposes. Analytical Methods, 2015.

Page | 93


ANALYSIS OF SOME PPCPs AND SELECTED ILLICIT DRUGS IN WATER BY USING

UHPLCORBITRAP MASS SPECTROMETRY Jalal T. Althakafy 1,2, Chadin Kulsing 1, Siti U. Mokhtar 1,3, Michael R. Grace

4, Philip J. Marriott 1

1 Australian Centre of Research on Separation Science, School of Chemistry, Faculty of Science, Monash University, Clayton, VIC 3800, Australia

2 Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, 21955 Makkah, Saudi Arabia

3 Faculty of Chemical Engineering and Natural Resources, Universiti Malaysia Pahang, 26300 Pahang, Malaysia

4 Water Studies Centre, School of Chemistry, Faculty of Science, Monash University, Clayton, VIC 3800, Australia

[email protected]

A method to analyse selected PPCPs and illicit drugs in some water samples was developed using ultra high pressure liquid chromatography (UHPLC) hyphenated with a Q-Exactive Plus Orbitrap mass spectrometer (Thermo Fisher Scientific). These samples were prepared for the analysis by performing solid phase extraction (SPE) using OASIS HLB 3cc (60 mg) cartridges. A Thermo Accucore column (2.1 mm×50 mm) packed with 2.6 μm C18 particles was used to first develop a separation and MS strategy, then to separate four water samples collected from various locations in Victoria, Australia. Gradient elution with acidic aqueous-acetonitrile mobile phases starting from 10 to 100%v/v acetonitrile proved adequate. The Orbitrap MS was used to detect these chemicals in either full scan at high resolution (70,000 FWHM) or MS/MS mode at low resolution (17,500 FWHM). The limit of detection was in the range 10 – 1000 pgmL-1. Validation of this method including linearity (ranged from 0.9875 to 0.9993), recovery (above 80% for most of the PPCPs); mass accuracy (below 2 ppm) was acceptable. The developed method was applied to quantify 13 PPCPs and identify some illicit drugs. The applied MS parameters such as automatic gain control (AGC) target and maximum injection time (IT) using Orbitrap were evaluated according to the number of points per peak, analyte peak areas and mass accuracy.

Page | 94


IN SITU STUDIES INTO THE CHARACTERISATION AND DEGRADATION OF BLUE BALLPOINT INKS BY DIFFUSE REFLECTANCE VISIBLE SPECTROSCOPY

Georgina Sauzier 1,2, Peter Giles 1, Simon W. Lewis 1,2 and Wilhelm van Bronswijk1

1 Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845, Australia.

2 Nanochemistry Research Institute, GPO Box U1987, Perth, Western Australia 6845, Australia

[email protected]

Despite the increasing trend toward electronic communication and transactions, written documents are still widely used in financial, legal and personal matters. The analysis and comparison of pen inks thus remains a highly relevant aspect of forensic investigations.

In this study, 35 blue ballpoint inks sourced from Western Australian retailers were deposited onto commercial copy paper and analysed using diffuse reflectance visible spectroscopy [1]. Principal component analysis showed that several pens were clearly distinguishable based on their visible spectra alone, although others exhibited overlap. Linear discriminant analysis was then used to build a chemometric model for ink classification. Using a separate validation set, 71.7% of spectra were correctly assigned to a specific pen, and a further 16.7% to the correct pen supplier. Analysis of six pen inks stored under different conditions found the inks largely remained unchanged for at least ten months when stored in the dark. However, two inks exhibited spectral changes after one week under ambient light, and all but one ink displayed changes within two months, resulting in altered predictions using the chemometric model. This may be useful in cases of alleged fraud, where it is suspected that an ink entry may have been altered using the same pen at a later date. Artificial ageing experiments found that both heat and ultraviolet light play a role in the ageing process, and that accelerated ageing using these factors gives a reasonable depiction of short-term ageing under natural conditions.

References:

[1] Sauzier, G; Giles, P.; Lewis, S. W.; van Bronswijk, W. In situ studies into the characterisation and degradation of blue ballpoint inks by diffuse reflectance visible spectroscopy. Anal Meth. 2015, 7 (12), 4892-4900.

Page | 95


REAL-TIME ELECTROCHEMICAL MONITORING OF COVALENT BOND FORMATION IN SOLUTION VIA

NANOPARTICLE–ELECTRODE COLLISIONSNa Kong 1, Da Li 2, Colin J. Barrow 1, Jingquan Liu 2, Wenrong Yang 1

1 Center for Chemistry and Biotechnology, Deakin University, 3217, VIC, Australia.2 College of Chemical Science and Engineering, Qingdao University, 266071, Qingdao,

China

[email protected]

Nanoparticle-Electrode collisions demonstrated that there are two kind of response: a cumulative cascade of current steps (‘‘staircase’’) and a serious of stochastic current jumps (‘‘spike’’) which are induced by permanent (a hit-n-stand model) and transiently (a hit-n-run model) adsorption respectively [1-3]. Based on this distinct current response, we describe an alternative electrochemical technique to monitor covalent bond formation in real-time using nanoparticle–electrode collisions [4]. To monitor the covalent bond formation, the gold microelectrode was modified with Lomant’s reagent (an ester with NHS) which could form the amido covalent bond via the amino groups from MP-11/rGO during the collision process. Then the MP-11/rGO nanosheets could stick onto the electrode surface and a “staircase” signal would be observed. As a control experiment, the gold microelectrode was coated with MPA reagents terminated with -COOH group. When MP-11/rGO nanosheet diffused to the MPA coated electrode surface, it was repelled away by the electrostatic repulsive and then a “spike” current change would occur. According to the staircase current, we could estimate the number of covalent bonds formed during the collision event.

Figure 1. (A) Schematic and (B) Current response of two types of collision events.

[1] Dick, J. E.; Hilterbrand, A. T.; Boika, A.; Upton, J. W.; Bard, A. J. Electrochemical detection of a single cytomegalovirus at an ultramicroelectrode and its antibody anchoring. Proc. Natl. Acad. Sci. U. S. A. 2015, 112, 5303-5308.

[2] Batchelor-McAuley, C.; Ellison, J.; Tschulik, K.; Hurst, P. L.; Boldt, R.; Compton, R. G. In situ nanoparticle sizing with zeptomole sensitivity. Analyst 2015, 140, 5048-5054.

[3] Kim, B.-K.; Boika, A.; Kim, J.; Dick, J. E.; Bard, A. J. Characterizing Emulsions by Observation of Single Droplet Collisions Attoliter Electrochemical Reactors. J. Am. Chem. Soc. 2014, 136, 4849-4852.

[4] Li, D.; Kong, N.; Liu, J.; Wang, H.; Barrow, C. J.; Zhang, S.-S.; Yang, W. Real-Time Electrochemical Monitoring Covalent Bond Formation in Solution via Nanoparticle-Electrode Collisions. Chem. Commun. 2015. DOI: 10.1039/C5CC06228D.

Page | 96


3D PRINTED ON-CAPILLARY PHOTOMETRIC DETECTION DEVICES: LOW COST DETECTOR

DESIGNS FABRICATED BY FDM PRINTING Farhan Cecil1, Petr Smejkal1, Pavel Nesterenko1, Michael C Breadmore1, Alan

Henderson2, Andrew Cole3, Rosanne M. Guijt4, Mirek Macka 1,

1 School of Physical Sciences and Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75, Hobart 7001, Australia

2.Faculty of Science ,Engineering and Technology, University of Tasmania, Private Bag 75, Hobart 7001, Australia

3.Faculty of Science ,Engineering and Technology, University of Tasmania, School of Mathematics and Physics, Private Bag 75, Hobart 7001, Australia

4.Faculty of Health , School of Pharmacy, University of Tasmania, Private Bag 75, Hobart 7001, Australia

[email protected]

Optical detection is the most commonly employed detection mode for a number of flow-through analytical techniques including capillary separation techniques such as capillary liquid chromatography (LC) and capillary electrophoresis (CE), as well as detection in process engineering.

In this project, a 3D printed on-capillary photometric detector is presented for the first time. Low-cost fused deposition modelling (FDM) 3D printers offer rapid prototyping of designs, which allows increased flexibility in the design process cycle (CAD design – 3D printing – experimental evaluation). This flexibility is particularly valuable in developing and modifying various designs to suit the needs.

In this work, we explored a novel design allowing the detector to be used with a broad range of outer diameters (o.d.) of the detection capillaries or tubings from 350 um-10,000 um, featuring a unique ‘slip-on’ side slot in the detector body, allowing installing the on-capillary detector without having to disconnect the capillary at one end first.

Using a under $3,000 FDM 3D printer with a nominal spatial resolution of 50 µm, slits at widths above ca. 150 µm could be fabricated, and a single-piece detector including the slit was fabricated within 3 hours. Fluorinated ethylene propylene (FEP) tubings of varying i.d. as well as o.d. were evaluated for the resulting detection performance.

The performance of the detector including the slit was tested by determining effective path length and stray light % for three detection tubing’s including 250, 500, and 750 µm i.d. The effective path length was calculated to be 166 µm, 356µm and 450µm and stray light was 18%, 4.5% and 2.5% for 250, 500, and 750 µm i.d detection tubing’s respectively. The detector was successfully tested for FIA analysis. These results shows that this detector shows satisfactory performance for all the tested tubing. Future avenues are further discussed.

Page | 97


METAL TOXICITY TO A POLAR MARINE ALGAE – DEVELOPMENT AND APPLICATION OF A ROBUST

TOXICITY PROTOCOLDarren J. Koppel 1,2,3, , Dianne F. Jolley 1, Francesca Gissi2, Merrin S. Adams2, and

Catherine K. King 3

1 School of Chemistry, University of Wollongong, Wollongong, NSW, AUS. [email protected]

2 CSIRO Land and Water, Sydney, NSW, AUS, [email protected],

3 Australian Antarctic Division, Hobart, Tasmania, AUS. [email protected]

[email protected]

The Antarctic environment is considered the last pristine wilderness. However, a hundred years of anthropogenic activity, including research, fishing, and tourism has resulted in pervasive and localised contamination to the Southern Ocean1. This contamination has been shown to adversely affect the community structure and diversity of algae in the marine ecosystem2. To prevent further contamination and facilitate remediation, a robust framework of polar specific water quality guidelines are required3. Ecotoxicology data is key to water quality guideline derivation; however, the methods used for ecotoxicological testing needs to be developed before the paucity of polar toxicology data can be addressed4.

This research developed and applied a robust metal toxicity test protocol to the polar marine algae, Cryothecomonas armigera. The parameters and conditions of OECD-compliant toxicity bioassays were modified to suit the different physiology and environment of polar algae. Flow cytometry was used to measure changes in cell growth, physiology, membrane permeability, and lipid production, in response to five common metal contaminants (Cu, Ni, Pb, Cd, and Zn). Furthermore, the bioavailablility of these contaminants in single and metal mixture treatments was investigated. The implications of these results to the development of polar specific water quality guidelines, and future polar environmental toxicology, is discussed.

1. Bargagli, R. Environmental contamination in Antarctic ecosystems. Sci. Total Environ. 400, 212–226 (2008).

2. Cunningham, L., Snape, I., Stark, J. S. & Riddle, M. J. Benthic diatom community response to environmental variables and metal concentrations in a contaminated bay adjacent to Casey Station, Antarctica. Mar. Pollut. Bull. 50, 264–275 (2005).

3. Batley, G. E. et al. Technical rationale for changes to the method for deriving Australian and New Zealand water quality guidelines values for toxicants. 46 (Commonwealth Scientific and Industrial Research Organisation, 2014).

4. Gissi, F., Adams, M. S., King, C. K. & Jolley, D. F. A robust bioassay to assess the toxicity of metals to the Antarctic marine microalga Phaeocyctis antarctica. Environ. Toxicol. Chem. (2015).

Page | 98


CREATING AND INTERPRETING HYPERSPECTRAL DATA FOR VEHICLE PAINTS

Caroline L. Watson 1, Rachel S. Popelka-Filcoff1, Jason R. Gascooke1, K. Paul Kirkbride1

1 School of Chemical and Physical Sciences, Flinders University, Sturt Road, Bedford Park. 5042, South Australia

[email protected]

Modern vehicle paint systems are complex and usually have a layered structure. Spectroscopic investigations of vehicle paints yield distinct spectra, characteristic of the constituent components of the paint layers. Different techniques offer different information on different layers of paint. Infra-red techniques offer information on the binders in the clearcoats while Ultra-violet and visible light sources offer information on the coloured pigments in the basecoat. By combining spectra from different instruments using different light sources, hyperspectral data can be obtained and a large amount of information about a paint sample can be interpreted from a single spectrum. Such a large spectral range also allows for simultaneous analysis of both the pigment and the clear-coat layers in modern paint systems. Typical hyperspectral data collated from several analytical instruments will be presented.

When applying laboratory analysis techniques to field-work, understanding how to interpret large spectral ranges can compensate for the loss of information from atmospheric interference. Certain spectral regions will no longer be able to offer viable information about the sample in question and therefore, the information that would have been obtained from those regions needs to be found elsewhere.

This research aims to identify spectral characteristics, or ‘fingerprints’, that can be used to correctly and consistently identify individual vehicles from paint samples or spectra obtained in the field for surveillance and forensic purposes.

Page | 99


MULTIDIMENSIONAL CHROMATOGRAPHY WITH HIGH RESOLUTION DETECTION FOR THE RESOLUTION OF

DISSOLVED ORGANIC MATTER (DOM)Sara Sandron1, Alfonso Rojas 1 , Noel Davies2, Richard Wilson2, Pavel Nesterenko1

and Brett Paull1

1Australian Centre for Research on Separation Sciences, University of Tasmania, Hobart, Australia2Central Science Laboratory, University of Tasmania, Hobart, Australia

[email protected]

Dissolved organic matter (DOM) in sea and freshwater represents a carbon reservoir comparable to atmospheric CO2 (respectively 624 and 750 Gigatonnes). CO2 is a primary product of DOM mineralisation, therefore an intimate link exists between this dissolved pool of carbon and the atmosphere. The complexity of DOM inhibits conventional chromatographic analysis (LC and GC) with common detectors, as little structural information can be obtained due to extensive co-elution. The chemical composition of DOM is extremely complex, containing various classes of compounds. These are polyfunctional, heterogeneous (amino acids, organic acids, lipids, phosphonates, carboxyl-rich alicyclic molecules (CRAM) and carbohydrate like precursors), polyelectrolytic, polydisperse in molecular weight (300-7000 Da) and in concentrations ranging from picomolar to micromolar.

In an effort to improve the current level of understanding of the complex nature of DOM, a multi-dimensional approach was employed. Eleven reversed-phase high-performance liquid chromatography (RP HPLC) C18 monolithic columns were connected in series to obtain a 110 cm long column with efficiency of 110,000 theoretical plates. The column was used to fractionate semi-polar and apolar components core components of DOM (i.e. CRAM). Fifteen fractions were isolated and further characterised by RP-HPLC with high resolution mass spectrometry (HRMS) detection. Upon formulae assignment, Van Krevelen diagrams revealed decreasing O/C ratios from earlier to later eluting fractions, and an increasing H/C ratio, indicative of an increasing degree of saturation. This information confirmed the successful fractionation of the major compositional materials within DOM in order of decreasing polarity.

The use of this chromatographic approach allowed the simplification of this very complex mixture to an extent that isomeric resolution was possible: homologous series of compounds were fractionated according to decreasing O/C and increasing H/C ratios. Different compounds with the same exact masses were separated, highlighting the presence of potentially hundreds of molecules for each molecular formula.

Page | 100

23rd RACI R&D Topics Conference 6-9 December 2015NOVEL METHODOLOGIES FOR THE EXTRACTION

OF PLANT METABOLITESTristan D. Kilmartin 1, Claire E. Lenehan 1

1 Flinders University, Bedford Park, 5042, SA, Australia

[email protected]

Naturally-occurring Deep Eutectic Solvents (NaDES), are composed of two or more naturally occurring compounds that, when combined, form a room-temperature liquid. Previously reported NaDES include mixtures of glucose and fructose, or glycerol and potassium carbonate. Researchers have proposed that NaDES could be a suitable replacement for organic-based solvents due to their hydrogen bonding capability, low flammability, vapour pressure, cost, and environmental impact [1]. This project explores the use of a range of different glycerol based NaDES in the ‘green’ extraction of bioactives from Calendula officinalis. Calendula officinalis was chosen due to its wide use in traditional European medicine to treat a range of conditions including conjunctivitis and burns[2]. Results from Ultra High Pressure Liquid Chromatography, total phenolic content (Folin-Ciocalteau’s Assay), and total antioxidant content (Sequential Injection Analysis-Chemiluminescence) tests show potential improved extraction when compared to typical water and ethanol based extracts.

1. Dai, Y., et al., Natural Deep Eutectic Solvents as a New Extraction Media for Phenolic Metabolites in Carthamus tinctorius L. Analytical Chemistry, 2013. 85(13): p. 6272-6278.

2. Ćetković, G.S., et al., Antioxidant properties of marigold extracts. Food Research International, 2004. 37(7): p. 643-650.

Page | 101


FORMATION OF PROTEIN “SUPER-ACIDS”: EXTENDING COMPLETE PROTEIN SEQUENCE

CHARACTERISATION BY TOP DOWN MASS SPECTROMETRY TO PROTEINS WITH MASSES

GREATER THAN 10 kDaMuhammad A. Zenaidee 1, William A. Donald 1

1 University of New South Wales, 2052, NSW, Australia

[email protected]

Electrospray ionisation (ESI) mass spectrometry (MS) has emerged as a central technique for protein sequence analysis. A key advantage of ESI is that protein ions can be formed in high charge states, which benefits many types of MS measurements. Protein ions in high charge states fragment more readily than those in low charge states to form more sequence ions, which results in higher sequence coverage. The Donald group has recently discovered that protein ions can be formed by ESI in higher charge states than previously thought possible based on the theoretical proton transfer limit.1-2 That is, highly charged gaseous protein ions that can readily protonate more basic solvent molecules from the ESI source can surprisingly survive the ESI process. Electron capture dissociation (ECD) of such highly charged protein ions (8.6 to 66.5 kDa) results in the formation of an extensive number of sequence ions, from which > 85% sequence coverage can be obtained from single tandem mass spectra of individual charge states.3 This extends near complete protein sequence coverage from single mass spectra to proteins with masses far larger than 10 kDa for the first time. To determine the effects that limit protein ion charging in ESI, we have measured the gas phase basicity of protein ions as a function of charge state. Surprisingly, highly charged proteins can readily protonate non-polar molecules and inert gases, including Ar, O2, and N2. These data indicate that protein ion charging in ESI can be significantly limited by proton transfer reactions with atmospheric gases, including N2 and O2. Because highly charged protein ion “super-acids” can readily protonate the gaseous solvent molecules of the ESI solution, such protein ions are likely formed in ESI by the ion evaporation mechanism, in which highly charged protein ions evaporate directly from the surfaces of highly charged droplets.

References:

[1] Zenaidee, M. A., & Donald, W. A. Extremely supercharged proteins in mass spectrometry: profiling the pH of electrospray generated droplets, narrowing charge state distributions, and increasing ion fragmentation. Analyst, 2015, 140(6), 1894-1905.

[2] Teo, C. A., & Donald, W. A. Solution additives for supercharging proteins beyond the theoretical maximum proton-transfer limit in electrospray ionization mass spectrometry. Analytical Chemistry, 2014, 86(9), 4455-4462.

[3] Zenaidee, M. A., & Donald, W. A. Electron capture dissociation of extremely supercharged protein ions formed by electrospray ionisation. Analytical Methods, 2015, 7, 7132-7139.

Page | 102


COUPLED COLUMN SELECTIVITY INTERPRETED USING SOLVATION PARAMETERS

Mohammad Sharif Khan, Chadin Kulsing, Sung-Tong Chin and Philip J. Marriott

Australian Centre for Research on Separation Science, School of Chemistry, Monash University, Wellington Rd., VIC 3168, Australia

[email protected]

The differential decompression of carrier gas by tuning the junction point pressure of a coupled column gas chromatographic system leads to a unique selectivity of the overall separation, tested here on a mixture of compounds with a wide range of polarity. This study demonstrates a pressure tuning (PT) GC system employing a microfluidic Deans’ switch located at the mid-point of the two capillary columns. This PT system allowed variations of inlet-outlet pressure differences of the two columns and the junction in a range of 52-17 psi for the upstream column and 31-11 psi for the downstream column. The peak shifting (differential migration) of compounds due to the pressure difference are related to a first order regression equation in a Plackett–Burman factorial optimisation study. The first (upstream) column decompression and second (downstream) column decompression alters the relative contributions of each column to the overall coupled column retention behaviours. Alkanes showed a linear retention shift whereas some polar compounds showed interaction effects that resulted in differences of elution order. The coupled column system selectivity was evaluated in terms of linear solvation energy relationship (LSER) parameters, and their relation with different pressure decompression effects has been constructed by applying multivariate principle component analysis (PCA). It has been found that the coupled column PT system descriptors provide a result that shows a clear clustering between commercially available columns. This is equivalent to that obtained from a conventional single-column GC analysis where the interaction energy contributed from the stationary phases can be significantly adjusted by choice of midpoint PT. This result provides a foundation for pressure differentiation for selectivity enhancement. The observed result is that optimised mixture resolution can be significantly enhanced through this simple PT approach, and LSER principles can assist to predict sample separation quality.

Page | 103


INNOVATIVE FLOW-ANALYSIS TECHNIQUES FOR THE TRACE DETERMINATION OF AMMONIA NITROGEN IN

MARINE WATERSLenka O’Connor Šraj 1,2, Ian D. McKelvie1, M. Ines G. S. Almeida 1, 2, Spas

D. Kolev 1,2

1 School of Chemistry, The University of Melbourne, 3010, VIC, Australia2Centre for Aquatic Pollution Identification and Management (CAPIM), The University of

Melbourne, 3010, VIC, Australia

[email protected]

A very sensitive and simple gas-diffusion flow method for the determination of ammonia nitrogen in marine waters has been developed. This method is automatic, requiring no manual sample or reagent introduction. The reagents used are non-toxic, show good stability over long periods of time, and their preparation is very simple.

The method developed is a modified stop-flow method, whereby the donor stream is continuously propelling a large sample volume through the donor channel of the gas-diffusion unit for a given period of time, during which the solution in the acceptor channel of the gas-diffusion unit is held static to accumulate ammonia diffusing through the membrane from the donor stream. This flow manipulation has improved the efficiency of analyte preconcentration in the acceptor solution, and allows to increase sensitivity, simply by increasing the sample volume propelled through the gas-diffusion cell.

The sensitivity of the system for a sample volume of 8.25 mL, propelled through the gas-diffusion cell at a flow rate of 3.36 mL min -1, is characterised by a limit of detection of 24 nmol L-1 at a sample throughput of 15 h-1. The linear range extends from 24 – 560 nmol L-

1 and the system has a dynamic range from 24 – 5,600 nmol L -1. The system repeatability is 0.35% (5,600 nmol L-1, n = 10) and 4.03% (56 nmol L-1, n = 10).

The method is one of the most sensitive photometric methods developed so far, and the simplicity and automation of this method as well as the possibility of varying sensitivity make it particularly suitable for long-term shipboard ammonia measurements or for the development of autonomous in situ logging devices.

Page | 104


Notes

Page | 105

table of contentsstatic1.squarespace.com/static/55432c00e4b067d5d2c8a25d/t... · web viewonline...

Documents