The Royal Australian Chemical Institute (RACI) 2014 National Congress for Chemistry, presentation

1. RACI- 2014 National Congress of Chemistry
Dr. Ahmed Khudhair Hassan
Ministry of Science & Technology
Environment & Water Directorate
Baghdad - Iraq

2.  Event Name: The Royal Australian Chemical Institute (RACI)
2014 National Congress.
 Event location: Adelaide / Australia.
 Event date: 7-12 December 2014.
 The meeting held every five years.
 There are over 1000 delegates at the meeting and many of these
are students and early career scientists.
 More than 550 Oral Presentations and more than 250 Poster
Presentations.

3.  Theme 1: Synthetic Chemistry.
 Theme 2: Fundamental Interactions in Chemistry.
 Theme 3: Advanced Materials.
 Theme 4: Chemical Health and Safety.
 Theme 5: Chemistry in Health.
 Theme 6: Chemical Analysis and Sensing.
 Theme 7: Community Engagement.

4. Theme 3: Advanced Materials
 OUTSTANDING ADSORPTION OF ARSENIC FROM CONTAMINATED
WATERS USING GRAPHENE/IRON OXIDE NANOPARTICLES-AEROGLES.
 NANOPOROUS LAYERED GRAPHENE HYDROGELS OF CONTROLLED
PORE SIZES: DESIGN, SYNTHESIS, CHARACTERIZATION AND
APPLICATIONS.
 GRAPHENE: A NOVEL MATERIAL FOR ELECTRONICS AND
OPTOELECTRONICS.
 LOW COST SOLUTION PROCESSED GRAPHENE-SILICON SOLAR.
 DEVELOPMENT OF POLYMERIC COATINGS TO PRODUCE ANTI-
BIOFOULING WATER TREATMENT MEMBRANES.
 ELECTROCHEMICAL FABRICATION OF CATALYTICALLY ACTIVE
ORGANIC SEMICONDUCTORS WITH ENVIRONMENTAL APPLICATIONS

5. Adsorption and reduction for heavy metal ions using Graphene
 Heavy metal ions, such as lead (Pb2+), cadmium (Cd2+), chromium
(Cr3+, Cr6+), mercury (Hg2+), copper (Cu2+) and arsenic (As3+), have
severe risks to environment and human health, and need to be removed
from soil and water.
 Graphene and its derivatives with high surface areas and many
functional groups, which benefit to the adsorption or preconcentration
of heavy metal ions, are given great attention in the present researches.
 Graphene oxide (GO) and reduced graphene oxide (RGO) with many
functional groups such as –O–, –OH, and –COOH, which can form
complexes with metal ions, are used to remove heavy metal ions.

6. (a) The synthesis and application for removing Cr6+of MCGNs.
(b) The comparison of adsorption mechanisms on GO and MCGN

7. Schematic illustration of silanization of Graphene

8.  Anti-biofouling polymeric coatings for polyamide (PA) thin
film composite (TFC) reverse osmosis (RO) (PA – TFC – RO)
membranes was used to desalt water.
 Poly ((2-methacryloxyethyl) trimethyl ammonium chloride)
(MTAC) modified membranes were tested for their ability to
permeate water and reject salt.
 Poly(MTAC) modified membranes were found to exhibit a
significant decrease in biofouling (93.2% after six days).
DEVELOPMENT OF POLYMERIC COATINGS TO PRODUCE
ANTI-BIOFOULING WATER TREATMENT MEMBRANES

9. SEM images of (a) CuTCNQ, (b)
AgTCNQ (d), CuTCNQF4, and (e)
AgTCNQF4
ELECTROCHEMICAL FABRICATION OF CATALYTICALLY
ACTIVE ORGANIC SEMICONDUCTORS WITH
ENVIRONMENTAL APPLICATIONS
The metal nanoparticle metal-7,7,8,8-
tetracyanoquinodimethane (MTCNQ)
materials have properties that allow them to
be employed in environmental remediation
processes such as the removal of harmful
Cr(VI) ions from aqueous solution using
environmentally friendly reductants at room
temperature with good reuse ability.

10. ION DETECTION USING POLYMER FUNCTIONALIZED ALGAN/GAN
TRANSISTOR DEVICES WITHOUT A REFERENCE ELECTRODE
 AlGaN/GaN high electron
mobility transistors
(HEMTs) are the result of
a 2-dimensional electron
gas layer (2DEG) that
forms at the AlGaN/GaN
interface.
 The conductivity of this
2DEG layer is sensitive to
charges on the surface,
thus forming the basis for
an ion sensor.
 For the first time that an
AlGaN/GaN device
without a reference
electrode can be used as a
Nitrate Sensor with the
appropriate ion selective
membrane.

11. ULTRA-POROUS MATERIALS FOR GAS
SEPARATION AND STORAGE APPLICATIONS
This presentation highlighted the recent experimental and
theoretical discoveries in the areas of H2, CH4 and CO2 storage plus
separations using ultra porous materials like Porous Aromatic
Frameworks (PAFs) and Metal-Organic Frameworks (MOFs).

12. Atomistic representation of (a) PAF-303 and (b) PAF-304 impregnated with
Li6C60. The PAF unit cell is highlighted in red, and Li6C60 is highlighted in blue
(lithium) and green (carbon).

13. (a) Hydrogen production and storage by renewable resource.
(b) hydrogen storage in metal doped carbon nanotubes

14. GRAPHENE OXIDE ENCAPSULATION OF BACTERIA USING VORTEX FLUIDS
 There is increasing research interest in
hybrid bio-nano materials, for example
in the hybridization of bacteria with
nanomaterials. Also of interest, is to
develop economically efficient and
environmentally friendly processing for
sustainable technologies for the future.
 A Vortex Fluidic Device (VFD) allows
rapid micro-mixing of reagents within
thin films in a rapidly rotating tube,
and we have used the microfluidic
device to prepare multilayer graphene-
algae and graphene oxide (GO)-algae
hybrid materials. In this study we
report on the wrapping of bacteria
Staphylococcus aureus and
Rhodococcus opacus with GO sheets
using the VFD.
GO wrapped bacteria using a VFD

15. SCALABLE CONTROL OF REACTIONS USING VORTEX FLUIDICS
 Flow chemistry offers scope for incorporating
scalability at the inception of the science, as part
of the drive towards developing more benign
technology, high in green chemistry metrics.
There is also the potential for moving beyond
diffusion control, in operating under turbulent
flow regimes.
 A vortex fluidic device (VFD) generates dynamic
thin films with intense shear, with the
microfluidic platform being distinctly different
to conventional channel based microfluidics
which usually operate under laminar flow
conditions.
 We have established that the VFD has
application in controlling chemical reactivity
and selectivity which is at the core of gaining
access to new compounds and materials.
Vortex fluidic device (VFD)

16. Vortex fluidic device (VFD)

17. Theme 4: Chemical Health and Safety
MODIFIED CLAYS AS EFFECTIVE ADSORBENTS
FOR REMOVAL OF WATER CONTAMINANTS
 Naturally occurring clay minerals have been
suggested as environmentally friendly
adsorbents due to their unique features:
(i) High cation exchange capacity (CEC).
(ii) Swelling properties.
(iii) High surface areas.
 For example, montmorillonite (MMT) is
readily available in several countries, and its
use as an adsorbent for the environmental
protection appears to be economically feasible.
 MMT is hydrophilic and unsuitable for the
removal of organic contaminants. When its
permanent negatively charged surface is
modified with quaternary ammonium cations
(QACs), it is converted to a hydrophobic
organoclay that can attract organic pollutants.

18. RECENT ADVANCES IN CONTAMINATED SITES REMEDIATION:
GREEN AND NANO-REMEDIATION TECHNOLOGIES
 Contaminated sites can pose significant risks to human
health and the wider environment, and the costs of
cleaning up contaminated sites are enormous. The US
EPA estimated in 2004 that over the following 30 years,
national clean-up costs could reach $250 billion, while the
estimate for Europe is around EUR 6 billion.
 As recently as the mid-1990s the most common
remediation strategy merely shifted the problem to later
generations by excavation and transport of contaminated
material to landfill sites (‘dig and dump’). This approach
is also ineffective once contaminants reach groundwater
and are transported away from the source.
 Over the past decade, the focus has shifted to technologies
that are sustainable and green (i.e. environmentally
beneficial in their application as well as their outcomes),
with nano-remediation also becoming more widespread.

19. In situ groundwater treatment by the hybrid fibre-optic photocatalytic system

20. CHEMICAL INVENTORY MANAGEMENT: IMPLEMENTING A
UNIVERSITY WIDE SYSTEM AT UNSW
 University of New South Wales (UNSW) is in 2014 implementing a new
system for the management of hazardous materials and dangerous goods
(HMDG).
 The system Enterprise Reagent Manager (ERM) has been developed by a US
based company called SciQuest and is being used at 70 Universities worldwide
mostly in the United States and Europe. It is used for tracking chemicals from
purchasing to disposal.
 This system will replace an older legacy system for Chemical ordering system
inventory (COSI)·
 The key component of this is SciQuest-ERM. This software will:
 Manage our chemical and other HMDG inventory in real time with the aid of
barcode scanners in each lab.
 Allow us to simultaneously search across all UNSW labs, our internal
stores and the catalogues of our key external vendors of HMDG's.
 Manage our external ordering of HMDG's, including safety warnings and
approvals.
 Manage purchasing from our internal store.

22. Theme 6: Chemical Analysis and Sensing
A HYBRID BIONANOSTRUCTURE OF GOLD NANOPARTICLES AND
MULTIWALLED CARBON NANOTUBES WITH ENZYMES FOR
ULTRASENSITIVE DETECTION OF CHOLESTEROL
 There has been an increasing interest
in recent years in the synthesis and
utilization of polymer
nanocomposites for fabrication of
biosensors.
 A novel strategy for co-entrapment of
MWCNTs and AuNPs in polypyrrole
(PPy) films and for utilization of their
synergistic effect for fabrication of
ultrasensitive cholesterol
amperometric nanobiosensors for
detection of free and total cholesterol
in blood samples.

23. MOBILE PHONE READABLE PAPER FLUIDIC
ELECTRO- CHEMILUMINESCENCE SENSORS
Microfluidic devices :
 Very small quantities of sample,
 Limit reagent use,
 High resolution and sensitivity,
 Low cost,
 Short times.
What is microfluidics? “It is the science and
technology of systems that process or
manipulate small (10-9 to 10-18 liters)
amounts of fluids, using channels with
dimensions of tens to hundreds of
micrometres.”

24. Glucose
assay
reagents
Color: from
colorless to
brown
(I− to I2)
Protein
assay
reagents
Color: from
yellow to blue
(NPB of TBPB
to proteins. )
Microfluidic paper-based analytical devices (μPADs)

25. μPADs for analysis of glucose and BSA (bovine serum albumin)
protein in urine.

26. Microfluidic Sensor

27.  The electrogenerated chemiluminescence
(ECL) is a phenomenon that a light emission
arises from the high energy electron transfer
reaction between electrogenerated species,
which is usually accompanied with the
regeneration of emitting species.
 A chemiluminescence reaction initiated and
controlled by the application of an
electrochemical potential.
 ECL reagent:
Tris(2,2’-bipyridyl)ruthenium(II), (Ru(bpy)3
2+)
 Good stability and ECL efficiency in aqueous
media,
 Favorable electrochemical properties,
 Compatibility with a wide range of analytes.
Electrogenerated Chemiluminescence (ECL)

28. Screen-printed Carbon
Electrodes
http://www.dropsens.com/en/screen_printed_electrodes_pag.html

30. Calibration curve between 0.5 mM and 20 mM for 2-(dibutylamino)ethanol
(DBAE) using paper microfluidic ECL sensor with mobile camera phone as the
detector. The magnitude of the ECL signal is proportional to the intensity of the
red pixels in the digital image.

31. GREEN CHEMISTRY
DEFINITION
Green Chemistry is the utilization of a set of principles that reduces or
eliminates
the use or generation of hazardous substances in the design,
manufacture and
application of chemical products *.
GREEN CHEMISTRY IS ABOUT
• Waste Minimisation at Source
• Use of Catalysts in place of Reagents
• Using Non-Toxic Reagents
• Use of Renewable Resources
• Improved Atom Efficiency
• Use of Solvent Free or Recyclable Environmentally Benign Solvent
systems
* Green Chemistry Theory & Practice, P T Anastas & J C Warner, Oxford University Press 1998

32. 1. Prevention
It is better to prevent waste than to treat or clean up waste after it has been created.
2. Atom Economy
Synthetic methods should be designed to maximise the incorporation of all materials used
in the process into the final product.
3. Less Hazardous Chemical Synthesis
Wherever practicable, synthetic methods should be designed to use and generate
substances that possess little or no toxicity to people or the environment.
4. Designing Safer Chemicals
Chemical products should be designed to effect their desired function while minimising
their toxicity.
5. Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g., solvents or separation agents) should be made
unnecessary whenever possible and innocuous when used.
6. Design for Energy Efficiency
Energy requirements of chemical processes should be recognised for their environmental
and economic impacts and should be minimised. If possible, synthetic methods should be
conducted at ambient temperature and pressure.
The 12 Principles of Green Chemistry (1-6)

33. The 12 Principles of Green Chemistry (7-12)
7 Use of Renewable Feedstocks
A raw material or feedstock should be renewable rather than depleting whenever technically
and economically practicable.
8 Reduce Derivatives
Unnecessary derivatization (use of blocking groups, protection/de-protection, and temporary
modification of physical/chemical processes) should be minimised or avoided if possible,
because such steps require additional reagents and can generate waste.
9 Catalysis
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
10 Design for Degradation
Chemical products should be designed so that at the end of their function they break down
into innocuous degradation products and do not persist in the environment.
11 Real-time Analysis for Pollution Prevention
Analytical methodologies need to be further developed to allow for real-time, in-process
monitoring and control prior to the formation of hazardous substances.
12 Inherently Safer Chemistry for Accident Prevention
Substances and the form of a substance used in a chemical process should be chosen to
minimise the potential for chemical accidents, including releases, explosions, and fires.

34. Less Hazardous Chemical Synthesis
 Disadvantages
 phosgene is highly toxic, corrosive
 requires large amount of CH2Cl2
 polycarbonate contaminated with Cl impurities
OH OH
Cl Cl
O
+
NaOH
O O *
O
* n
Polycarbonate Synthesis: Phosgene Process

35. Less Hazardous Chemical Synthesis
OH OH
+ O O *
O
* n
O O
O
 Advantages
 diphenylcarbonate synthesized without phosgene
 eliminates use of CH2Cl2
 higher-quality polycarbonates
Polycarbonate Synthesis: Solid-State Process

36. Polymers from Renewable Resources:
Poly(lactic acid)
http://www.natureworksllc.com/corporate/nw_pack_home.asp

37. Raw Materials from Renewable Resources:
The BioFine Process
O
HO
O
Paper mill
sludge
Levulinic acid
Municipal solid waste
and waste paper
Agricultural
residues,
Waste wood
Green Chemistry Challenge Award
1999 Small Business Award

38. Levulinic acid as a platform chemical
O
HO
O
O
H2N
OH
O
O
HO
DALA (-amino levulinic acid)
(non-toxic, biodegradable herbicide)
O
HO
O
OH
C
CH3
C
H2
C
H2
C
O
OHHO
Diphenolic acid
Acrylic acid
Succinic acid
O
THF
O
MTHF
(fuel additive)
HO
OH
butanediol
O
O
gamma
butyrolactone

39. Green Chemistry Is About...
Waste
Materials
Hazard
Environmental Impact
COST
Risk
Energy

40. Catalysis
Process
Intensification
Separation
Processes
Energy
Efficiency
Solvent
Replacement
Safer Reactions
& Reagents
Use of
Renewable
Feedstocks
Waste
Minimisation
Some Aspects of Green Chemistry
Green
Chemistry

41. Multidimensionality in Gas Chromatography
A typical multidimensional separation GC system, combined with
multidimensional analysis using spectroscopic detection

42. CRYSTALLINE SPONGE METHOD: X-RAY STRUCTURE
ANALYSIS WITHOUT CRYSTALLIZATION

43. The Epsilon 3XLE handles
a wide variety of sample
types, including solids,
pressed and loose
powders, liquids and
filters. It performs non-
destructive quantitative
analysis of elements
from carbon (C) to
americium (Am), in
concentrations from
100% down to sub-ppm
levels, on samples
weighing anything from
a few milligrams to
kilograms.
XRF- Ready for any sample type

50. Dr Ahmed Khudhair Hassan would like to thank
the Chemical Security Engagement Program
(CSP) sponsored by the Department of State of
the USA and managed by the CRDF Global for
all the financial and administrative support.
Acknowledgments