DOI: 10.1002/asia.
201700598 Community Report
Silicon Chemistry
Advanced Silicon Chemistry in Australia: Forming Strong Links
with Asia
Stephen Clarke,*[a] Kim-Anh Thi Nguyen,[b] Elda Markovic,[a] Neil Trout,[a] Milena Ginic-
Markovic,[c] Janis Matisons,[d] Michael Owen,[e] Daniel Graiver,[f] Agus Hadi
Santosa Wargadipura,[g] Sudirman Habibie,[g] Dwi Gustiono,[g] Bok Ryul Yoo,[h] and
Joe Mifsud[a]
Abstract: This paper details Australian commercial and aca-
demic silicon research. Areas of interest include silicon
metal, polysiloxane polymers, copolymers, cyclics, emulsions,
microemulsions, silanes, silane coupling agents, sol-gel
chemistry and water-treatments, porous silicon, polysiloxane
degradation, silicon hydrogel contact lenses, silanolate syn-
thesis, siloxane interfacial polymerisation, hydrosilylation,
polysiloxane electrolytes for lithium ion batteries, silanes for
PBX materials, octafunctionalized polyhedral oligomeric sil-
General Overview
High-cost, specialised silicon materials, including silicone poly-
mers, have reduced in price, over the years and, in many in-
stances, are now competitive in cost and application, with
counterpart petrochemical derived, organic materials and poly-
mers. Clarson has identified the growth of silicon options, from
a 25 % increase in annual demand for silicon used in solar
panel applications, which has been the driving force, pushing
down the cost of many silicon applications.[1]
Silicon materials have been used for a wide variety of appli-
cations, and Australia has played a keen role in the develop-
[a] Dr. S. Clarke, Dr. E. Markovic, Dr. N. Trout, J. Mifsud
Associate (Research & Development: Polymer Chemistry)
COOE Pty Ltd.
46/40 W Thebarton Rd, Thebarton, South Australia, 5031 (Australia)
E-mail: stephen@cooe.com.au
[b] Dr. K.-A. T. Nguyen
Information, Technology, Engineering and the Environment (Divisional
Office)
University of South Australia
Mawson Lakes Blvd, Mawson Lakes, South Australia, 5095 (Australia)
[c] Dr. M. Ginic-Markovic
Future Industries Institute
University of South Australia
[d] Prof. J. Matisons
Vice President
Silar LLC
300 N 3rd St, Wilmington, North Carolina 28401 (USA)
[e] Dr. M. Owen
Scientist Emeritus
Dow Corning Corporation
Midland, MI (USA)
Chem. Asian J. 2017, 12, 1123 – 1152
sesquioxanes (POSS), POSS hybrids, sol-gel hydrogenation
catalysts, silane modification of silica, sol-gel energy storage,
silicate grout stabilisation, GeoPolymer concretes, aerogel in-
sulating foams, “Phaco-Ersatz” Accommodating Gel—Intraoc-
ular Lens technologies. Strong collaborative opportunities, in
silicon, with Asia, exist with organisations such as: 1) The
Asian Silicon Society and 2) The Agency for the Assessment
and Application of Technology (BPPT) Indonesia.
ment of many new silicon materials. Silicon materials are used
for a wide variety of applications including: solar panels for
electrical energy; applications in specialist materials; photon-
ics; environmental applications; metallurgical applications and
surface modification.[2]
Although silicon materials and their chemistry were com-
mercially introduced to Australia by the Dow Corning Corpora-
tion in 1964 and have been intensively studied in Australia, by
academics, since the 1980s. Most Australian silicon technolo-
gists working in the field aligned their allegiances to other sci-
entific fields and technologies. Therefore, it is true to say that
apart from a few genuine, silicon trail-blazers, many Australian
[f] Prof. D. Graiver
Department of Macromolecular Chemistry
Case Western Reserve University
10900 Euclid Ave, Cleveland, Ohio 44106 (USA)
[g] Dr. A. H. S. Wargadipura, Dr. S. Habibie, Dr. D. Gustiono
Centre for Material Technology
Agency for the Assessment and Application of Technology (BPPT)
Jalan MH Thamrin 8, Jakarta (Indonesia)
[h] Prof. B. R. Yoo
Materials Architecturing Research Center, Silicon Chemistry Team
Korea Institute of Science and Technology (KIST)
Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Republic of Korea)
The ORCID identification number(s) for the author(s) of this article can be
found under https://doi.org/10.1002/asia.201700598.
This manuscript is part of a special issue on advances in silicon chemistry.
Click here to see the Table of Contents of the special issue.
1123 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

silicon technologists used their silicon expertise to assist the
development of other non-silicon focused technologies, and
so failed to classify themselves as silicon scientists. This, un-
fortunately, hampered the recognition of silicon chemistry as
a genuine science in Australia, and perhaps even international-
ly damaged Australia’s recognition in this field. For example,
many using silicon chemistry technologies might classify them-
selves as polymer scientists, nanotechnologists, or maybe even
medical device technologists, and so on, but not as silicon sci-
entists per se. This meant that unlike America, Europe or Asia,
there has been no driving force in Australia, for those actively
involved in silicon chemistry and technology that would devel-
op an active silicon community, engendering an inherent
strength in Australian research activity in the eyes of academia,
industry and government.
This paper focuses on the progressive development of Aus-
tralian silicon science and technology over the ages. Therefore,
it would be remiss not to mention some of the Australian trail-
blazers who have worked tirelessly in the field, regarding
themselves as genuine silicon scientists, but not receiving the
level of local and international acclaim for their achievements,
as deserved.
Australian Silicon Industry Overview
Dow Corning
It would be a grave disservice to Australian silicon technology
not to mention the important, role played by the Dow Corning
Corporation, in setting up Dow Corning Australia Pty Ltd in
1964 and establishing Australia’s largest polysiloxane manufac-
turing facility in Blacktown, New South Wales. The Australian
site did not manufacture polysiloxanes, per se, but rather for-
mulated them into useful products. Also, the Blacktown labora-
tory could best be described as a development and R&D facili-
ty. At that site, Dow Corning manufactured a wide range of ad-
vanced silicone fluids, polysiloxane sealants, emulsions and mi-
croemulsions. It was a sad day for Australian silicon technology
when in the early 2000s, Dow Corning closed its Blacktown
manufacturing and research facility to establish a new “sales-
only” outlet, supplying overseas manufactured silicone product
from a new site, at a University Technology Park, in North
Ryde, New South Wales. Shortly before this closure Dow Corn-
ing Corporation engaged with Professor Janis Matisons, to
engage in a wide-ranging, nine-year, series of research projects
investigating interfacial copolymerisation of silicon polymers
from 1995 through to 2004. A summary of the key players
from Dow Corning instigating these projects is identified
below:
Interfacial Polymerisation project with Dow Corning
Dr. Michael Owen—from the Dow Corning, Central Research
Laboratories in Midland, Michigan, USA partnership with Dr.
Janis Matisons (University of South Australia) established in
1995 a small student exchange research project in Michigan
Dow Corning.[3] This led to a larger joint Australian Govern-
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ment/Dow Corning funded PhD research project, undertaken
by Dr. Stephen Clarke at the University of South Australia. Fol-
lowing this an even larger silicone research project, funded by
Dow Corning and the Australian Government was conducted,
initially at University of South Australia, then at Flinders Univer-
sity.
Dr. Daniel Graiver—from the Dow Corning, Central Research
Laboratories in Midland, Michigan, USA in discussion with Pro-
fessor Janis Matisons and Dr. Michael Owen, provided the con-
cept and project guidance for the Australian/ Dow Corning in-
terfacial polymerisation research project, which ran from 1995
to 2004.[3]
Dr. Richard Grant- from the Dow Corning, Research Labora-
tories in Blacktown, New South Wales, Australia, provided the
Australian Dow Corning industry component for the research
collaboration between Australia and Dow Corning, for this im-
portant interfacial polymerisation project. Dr. Grant was re-
sponsible for much of the more fundamental silicon research
conducted, in Australia by Dow Corning.
Simcoa Operations
It would also be remiss not to mention the role of Simcoa Op-
erations Pty Ltd,[4] based in Bunbury, Western Australia, a com-
pany which claims to manufacture some of the world’s best
quality silicon in the world. They produce around
50 000 tonnes annually, exporting 95 % of this to a diverse
range of overseas markets, with customers in Japan, Germany,
United Arab Emirates, USA, and New Zealand.
Flexichem
Oddly, the one person, who it could be argued, single-handed-
ly made the greatest impact in to Australian silicon science
commercially, is virtually unknown and unrecognised for his
achievement and this is Dr. Geoffrey Swincer. He was an aca-
demic research scientist working in the Chemistry Department
at the South Australian Institute of Technology’s (SAIT) Levels
campus in the 1980s, now the University of South Australia
(UniSA). This campus has since been renamed the Mawson
Lakes campus. Dr. Swincer established the Institute’s Polymer
Science Group. While leading this group Dr. Swincer secured
an Australian Research Council (ARC) grant to work on silicone
polymers. Recognising the potential of this emerging silicon
technology, which was virtually unknown in Australia, on com-
pletion of this research project, Dr. Swincer left the Institute in
1990 and established a new spin-out company—Flexichem Pty
Ltd.,[5] manufacturing advanced silicone polymers. The compa-
ny remained based at SAIT’s Levels campus, employing re-
searchers from the Institute’s Polymer Science Group. The com-
pany built two sheds at the back of the Polymer laboratory,
with one shed being used as Flexichem’s factory and the
other, the company’s raw material and finished product stor-
age shed. There was a fascinating symbiotic working arrange-
ment, established between SAIT and Flexichem, with the com-
pany funding the Institute’s Polymer Science Group. In turn
the Polymer Science Group exclusively supported the compa-
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ny’s ongoing research activities, developing many new polysil-
oxane products. In 1991 SAIT became the University of South
Australia (UniSA). Around this time Flexichem also needed to
expand, so moved off-campus and established a much larger
manufacturing factory, and its own research facility at Wing-
field, South Australia. At that point in time Flexichem, effective-
ly ceased intimate connection with the University. Many Poly-
mer Science Group members, left the University and trans-
ferred to Wingfield, but some also remained at UniSA, to for-
mally join what became the University’s Polymer Science
Group, led by Flexichem’s former Technical Manager—Dr. Janis
Matisons. Flexichem has continued to prosper. At one stage
Flexichem was manufacturing sol-gel, hard coats for Sola Opti-
cal, a company based at Lonsdale, South Australia. At the time,
Sola Optical was the wold’s largest manufacturer of plastic
spectacle lenses. Flexichem also manufactured, under licence,
a range silicone products, which were sold by GE Silicone as
GE Silicone products. Currently Flexichem is Australia’s only
manufacturer of polysiloxane products and is still based at
Wingfield. The company operates quietly, but extremely suc-
cessfully, producing its own range of excellent quality, compet-
itively priced silicone polymers, silicone emulsions and microe-
mulsions.
Advanced Molecular Technologies Pty Ltd founded by Sebas-
tian Marcuccio in May 2005,[6] is a specialist biotech company
which has focused on the development and commercialisation
of new products. Whilst the company has focused on boranes
and organoboron compounds he has also made important
contributions to silane development in Australia, making over
200 silanes and organosilane products over the past 12 years.
Ceramisphere Pty Ltd was established in January 2007, as
a fully owned subsidiary of ANSTO with the mission to com-
mercialise ANSTO’s sol-gel encapsulation technology.[7] Dr.
Christophe Barb8, now CEO of the company and was involved
in its formation, at the outset. The company is producing con-
trolled release drugs encapsulated in sol-gel based silica core–
shell materials.
Australian Silicon Research—Academic Over-
view
Professor Janis Matisons
This Flexichem discussion, immediately leads to a conversation
about the enormous impact Dr. Janis Matisons, now Professor
Matisons, made to silicon science research, in Australia, espe-
cially in the academic space. When Flexichem was based at
UniSA, Dr. Matisons was the company’s Technical Manager, but
when Flexichem left the University Dr. Matisons elected to stay
at the University and take over the Group Leadership role of
UniSA’s Polymer Science Group. Single-handedly, and virtually
without reward, or genuine recognition in Australia for his in-
dustry related silicon achievements, Dr. Matisons, rapidly
moved through the academic system and became a full Profes-
sor.
It was around this time Professor Matisons began to put
Australian silicon science on the academic world-map. For the
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Community Report
first time, he started to gain international recognition for Aus-
tralian academic silicon science research activities. To put this
achievement in perspective, when Mrs Milena Ginic-Markovic
(now Dr. Ginic-Markovic) and the author joined this research
group as “wide-eyed” PhD students in February 1996, there
were only five researchers in this academic group, following
the split with Flexichem. Dr. Matisons, as the new Group
Leader, had only just returned to Australia, following a lengthy
trip to Europe and the USA establishing new, key international
industrial and academic collaborations for the UniSA. He estab-
lished an important collaboration with the Abo Akademi, de-
veloping and improving the understanding of silane coupling
agents for glass fibre composite materials. He also established
a collaboration with Dow Corning Corporation, in Midland
Michigan, investigating new polysiloxane copolymers, which
also led to new exciting academic research projects for Austral-
ia in silicon chemistry. This helped to expand and develop the
Polymer Science Group. In 1996, this group, consisted of
Arthur Provatas as a PhD research student, Peter Folland and
Jun Mu—both Master’s degree students and Dr. Leanne Britch-
er—a recent PhD graduate and post-doctoral researcher.
It was amazing to watch this research group grow and
expand rapidly over the next six years. By 2002, this Research
Group had grown to become the largest and most well-
funded academic polymer research group, in Australia, having
some 40 researchers. In 1996 Professor Matisons obtained his
first ARC organosilicon polysiloxane project with Dow Corning,
which funded the author’s PhD research program. Then in
2000, he obtained a much larger research project with Dow
Corning, expanding the earlier silicon polymer research gains.
Professor Matisons attained many other projects, many in part-
nership with industry, but others also academic in nature.
Despite these achievements and having been promoted to
a full Professor, by the University, true recognition and support
by the University was absent. Professor Matisons then trans-
ferred to Flinders University, in South Australia in early 2002 as
Professor of Nanotechnology. Some former UniSA team mem-
bers remained at UniSA and others transferred to Flinders Uni-
versity. Not surprising, to those knowing Professor Matisons’
drive and passion for Australian silicon science, he rapidly re-
built this new research team at Flinders to around twenty-five
members, obtaining major funding for projects in sol-gel,
silane anti-corrosion coatings and reverse osmosis desalination,
as well as many other academic research projects.
Professor Matisons gained international recognition for
these achievements, particularly in the silicon chemistry space,
and was invited onto the eminent ISOS International Advisory
Board, He also became Chief Editor of the Silicon Chemistry
scientific journal and Series Editor for Springer’s Advances in
Silicon Science book series. However, academic recognition
and reward, in Australia, for this outstanding foresight and suc-
cess was limited. Rather than acknowledging these achieve-
ments, some senior academics were not supportive, which
harmed the progressive development of academic silicon re-
search in Australia. Professor Matisons then accepted a high-
profile role in one of the most recognised international silicon
companies, based in the USA—this being Senior R&D Manager
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for Gelest. Then in the second half of 2016 he accepted the il-
lustrious position as Vice President of the influential American
silicon company Silar Laboratories,[8] and currently holds this
role.
Emeritus Professor Graeme George
From an academic perspective, it would be negligent not to
discuss the ground-breaking work conducted by Emeritus Pro-
fessor Graeme George[9] from the Queensland University of
Technology, who perhaps may have regarded himself more as
polymer scientist, having extensive expertise in polymer degra-
dation. In his early research career, during the late 1990s and
early 2000s, Professor George contributed greatly to the under-
standing of the degradation of silicone polymers. His work
emanated from research investigating the stability of silicone
based high-tension electrical insulators. In the second half of
2000 and beyond, Professor George turned his considerable sil-
icone expertise towards developing and understanding the
performance of silicone based medical grade gel sheets for the
treatment of burns.
Professor Nicolas Voelcker
Similarly, working more from a medical device perspective, Pro-
fessor Nico Voelcker[10] gained a considerable understanding of
various porous silicon technologies and silane coupling agents,
principally for the development of new medical device applica-
tions. He was trained in Germany, then in 1999 transferred to
the USA, working for the Scripps Research Institute, La Jolla,
California, working there until 2001. He then transferred to
Adelaide, Australia joining Flinders University, working there as
an academic scientist until 2012. From 2012 to 2016 he trans-
ferred to University of South Australia, becoming the Strand
Leader and Lloyd Sansom Chair in Biomaterials Engineering
and Nanomedicine at that University’s Future Industries Insti-
tute. However, at the beginning of 2017, Professor Voelcker
transferred his research team to one of Australia’s largest and
most eminent Universities, this being Monash University, in Vic-
toria, Australia.
The “Phaco-Ersatz” Accommodating Gel—Intraocular Lens
Technology (AG-IOL) project
Following Professor Matisons’ departure to the States, Dr.
Clarke, when leading the Materials and BioEnergy Group at
Flinders University, took on more new silicon science academic
research opportunities at the University. Despite being highly
trained in organosilicon copolymer chemistry, at PhD research
level,[11] Dr. Clarke from 2002 to 2010, focused much of his re-
search activity on polymers, biofuels, water treatment and the
chemical biorefinery. However, following Professor Matisons’
departure to the USA, new academic research opportunities
arose in silicon science.
The Brien Holden Vision Institute (BHVI), based at the Univer-
sity of New South Wales (UNSW) in partnership with Australia’s
CSIRO and other international partners, developed the first
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long-wearing, oxygen permeable, silicon-hydrogel contact lens.
This invention was patented in 1998[12] and commercialised by
Ciba Vision, now a Division of Novartis—a global healthcare
company based in Basel, Switzerland, with a history going
back more than 150 years. Although not commercialised and
manufactured in Australia, sales of this technology are claimed
to be in the order of $7 billion annually, with royalties going
back to the Vision CRC (formerly CRC—ERT) based in the BHVI
having a total value of $300 million AUD. BHVI then engaged
Dr. Clarke’s team, on three successive research projects, valued
at $500 000 AUD (cash), at Flinders University, to work on their
“Phaco-Ersatz” accommodating gel—intraocular lens (AG-IOL)
academic research project. These academic research projects
being funded by the Australian Government’s—Vision CRC
Scheme.
With increasing academic activity in silicon focused silicone
polymer and sol-gel research, Dr. Clarke bid twice for the right
to Chair in Australia, the International Symposium on Silicon
Chemistry (ISOS). The two bids were lodged in 2011 at McMas-
ter University[13] and 2014 in Berlin,[14] to host ISOS XVII and
ISOS XVIII in 2014 and 2017 respectively. Although unsuccess-
ful with both ISOS bids. Dr. Clarke was invited to attend the
5th Asian Silicon Symposium (ASiS-5) at Jeju, South Korea, Octo-
ber, 2015.[15] Recognising the contribution made to Australian
silicon science, by Dr. Clarke, the influential Asian Silicon Soci-
ety (ASiS) invited him to join the International Advisory Board
of the Society (ASiS). Dr. Clarke was also invited to become
a Fellow of the influential Royal Australian Chemical Institute
(RACI). In addition, the ASiS Board invited Dr. Clarke to Chair
the 7th Asian Silicon Symposium (ASiS-7) in Australia in 2019.
This is the first time an ASiS conference will be held outside of
Asia, and currently plan to run the conference at the interna-
tionally renowned Mackay Entertainment and Convention
Centre (MECC). Dr. Clarke was also invited to speak at the
world’s largest silicon conference—ISOS XVIII in August
2017.[16] He was then asked to submit a manuscript to the
highly-regarded Wiley scientific journal Chemistry—An Asian
Journal, relating to the ISOS XVIII Invited conference paper.
Future Collaboration with BPPT (Agency for the Assessment
and Application of Technology)—Indonesia
Advanced Medical Devices have traditionally relied heavily on
silane chemistry and silicone polymers. The “Phaco-Ersatz” Ac-
commodating Gel—Intraocular lens (AG-IOL) research project,
conducted by Dr. Clarke’s team and funded by the BHVI at
UNSW, is one such project. Knowing of Dr. Clarke’s research in
this field, the Agency for the Assessment and Application of
Technology (BPPT),[17] based in Jakarta, Indonesia sought to es-
tablish a research collaboration with COOE Pty Ltd, and Dr.
Clarke. Catalysed by prior joint publications,[18–21] this important
key Asian initiative has been spear-headed by:
· Dr. Agus Hadi Santosa Wargadipura.—Centre for Material
Technology, Agency for the Assessment and Application of
Technology (BPPT) Indonesia
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· Dr. Sudirman Habibie—Senior Researcher in Centre of Tech-
nology for Material Technology, Agency for the Assessment
and Application of Technology (BPPT) Indonesia
A Memorandum of Understanding and an Implementation
Agreement has been signed by the Chairman of BPPT (Indone-
sia) and the Director of COOE Pty Ltd (Australia) on the 21st of
February 2017 to engage in research and education initiatives,
which will also include collaboration in silicon materials, with
an aim towards polymers and advanced medical devices.
Dr. Gustiono and Dr. Wargadipura at the Centre of Technolo-
gy for Material Technology (PMT) in BPPT have also established
a vibrant research project for the casting of metallurgical
grade of poly-crystalline silicon ingot using the Direct Solidifi-
cation System. Figure 1 shows the Direct Solidification System
and Figure 2 the conversion of silicon metal flakes to solid cast
silicon, using the Direct Solidification System.
The cast silicon ingots are being used to manufacture a new
silicon solar panel technology and Australian silicon scientists,
from COOE Pty Ltd, will be looking to engage with this excit-
ing new Asian silicon development from Indonesia.
Figure 1. Advanced alloy analyser at the Centre for Material Technology Lab-
oratory in BPPT, Indonesia.
Figure 2. Silicon alloy synthesized at the Centre for Material Technology Lab-
oratory in BPPT, Indonesia.
Asian Silicon Society
The Asian Silicon Symposium (ASiS) takes place in Asia bienni-
ally and has previously been hosted by the Silicon Societies of
Japan, Korea, and China. At the ASiS meeting, all aspects of sili-
con chemistry are presented and discussed by both professio-
nals and students who are working in academic and industrial
Chem. Asian J. 2017, 12, 1123 – 1152 www.chemasianj.org
Community Report
fields in Asia. The ASiS meeting is open to the world’s silicon
community. Previous ASiS meetings have been successfully
held in Miyagi, Japan in 2007 (ASiS-1), at Jeju, Korea in 2008
(ASiS-2), at Hangzhou, China in 2010 (ASiS-3), at Tsukuba,
Japan in 2012 (ASiS-4) and at Jeju, Korea in 2015 (ASiS-5). The
International Symposium on Applied Silicon Chemistry (ISASC)
is held triennially and was founded by the Research and Edu-
cation Center for Advanced Silicon Materials (RECASM), which
is affiliated with Yonsei University and KCC. After the 1st ISASC
at Yonsei University in Wonju in 2010, the Korean Silicon Soci-
ety (KSiS) was established in 2011. Subsequently, it became the
host of the ISASC, which provides a forum for scientists inter-
ested in silicon materials to present and discuss all aspects of
applied silicon chemistry. The 2nd ISASC was successfully held
at the Korea Institute of Science and Technology (KIST) in
Seoul on October 24–25, 2013.
This scientific paper summarizes key industry contributions
to Australian silicon chemistry and technology achievements,
including research by various Australian academic groups plus
research conducted by the Clarke and Matisons research
teams, when at UniSA and Flinders University, from 1995 to
October 2015. Also included is an overview of the science re-
lated to ‘Phaco-Ersatz“ Accommodating Gel—Intraocular Lens
research.[22]
This paper also identifies future strong collaboration oppor-
tunities currently being evolved with Asia, including organisa-
tions such as: 1) The Asian Silicon Society and 2) The Agency
for the Assessment and Application of Technology (BPPT) Indo-
nesia.
Silicone Polymer Research
Some interesting research projects which have been conduct-
ed over the past few decades in Australia are set out below:
(1) Synthesis of block siloxane copolymers using dipotassi-
um siloxanediolate monomer
In this research dipotassium poly(methylphenylsiloxanedio-
lates[3] of various molecular masses were synthesised, as shown
in Scheme 1:
A novel interfacial polymerisation procedure was then used
to react dipotassium poly(methylphenylsiloxanediolate with
1,5-dichlorohexamethyltrisiloxane to produce a series of poly(-
methylphenylsiloxane)-block-poly(dimethylsiloxane) block co-
polymers (Scheme 2).
Figure 3 a and 3 b show GPC traces of poly(methylphenylsi-
loxane)-block-poly(dimethylsiloxane) block copolymer, pre-
pared by unstirred interfacial polymerisation of 1,5-dichloro-
hexamethyltrisiloxane, reacting with dipotassium poly(methyl-
Scheme 1. Synthesis of dipotassium siloxanediolate monomer.
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Scheme 2. Interfacial polymerization using dichlorosiloxane and disiloxane-

diolate monomer.

Figure 4. a) 29Si NMR spectra of poly(methylphenylsiloxane)-block-poly(di-

methylsiloxane) block copolymer prepared from KO[(C6H5)(CH3)SiO]5.5K and
1,5-dichlorohexamethyltrisiloxane, having Mn = 16.020 and PD @6.0.
b) 29Si NMR spectra of poly(methylphenylsiloxane)-block-poly(dimethylsil-
oxane) block copolymer prepared from KO[(C6H5)(CH3)SiO]8.3K and 1,5-di-
chlorohexamethyltrisiloxane, having Mn = 4818 and PD@2.0.

Figure 4 a and 4 b shows 29Si NMR spectra of poly(methyl-

phenylsiloxane)-block-poly(dimethylsiloxane) block copolymer,
prepared by unstirred interfacial polymerisation of 1,5-dichloro-
hexamethyltrisiloxane, reacting with dipotassium poly(methyl-
phenylsiloxanediolate, respectively, having nominal chemical
structures of KO[(C6H5)(CH3)SiO]5.5K and KO[(C6H5)(CH3)SiO]8.3K.

(2) Synthesis of dipotassium dimethylsilanediolate monohy-

drate and siloxane copolymers
Dipotassium dimethylsilanediolate monohydrate,[23, 24] was syn-
Figure 3. a) GPC of poly(methylphenylsiloxane)-block-poly(dimethylsiloxane) thesised for the first time and was fully characterized by a varie-
block copolymer prepared from KO[(C6H5)(CH3)SiO]5.5K and 1,5-dichlorohexa- ty of techniques.
methyltrisiloxane, having Mn = 16.020 and PD@6.0. b) GPC of poly(methyl-
The synthesis was achieved by reacting one mole of
phenylsiloxane)-block-poly(dimethylsiloxane) block copolymer prepared
from KO[(C6H5)(CH3)SiO]8.3K and 1,5-dichlorohexamethyltrisiloxane, having 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane (D4) with eight
Mn = 4,818 and PD@2.0. moles of potassium hydroxide, on a stoichiometric basis, in
dried toluene using a Dean–Stark apparatus, as shown in
phenylsiloxanediolate, respectively, having nominal chemical Scheme 3.
structures and potassium contents (by mass) of (1):
KO[(C6H5)(CH3)SiO]5.5K (potassium content 9.2 %) and
(2) KO[(C6H5)(CH3)SiO]8.3K (potassium content 6.4 %). Number
average Mn and polydispersity (PD) data for these two copoly-
mers were:
1. Mn = 16.020 and PD@6.0
2. Mn = 4,818 and PD@2.0 Scheme 3. Synthesis of dipotassium dimethylsilanediolate monohydrate salt.

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The reaction was conducted at 110 8C, with the Dean–Stark
apparatus to remove the excess water. The material obtained
was highly deliquescent, containing less than 1 % unreacted
D4.
A complex series of analysis techniques, such as acid/base ti-
tration, powder XRD, FTIR (DRIFT), NMR (proton, carbon and
silicon) in D2O, microchemical analysis (carbon and hydrogen)
and ICP (silicon and potassium) analysis confirmed this new
compound existed as the monohydrate salt.
Sophisticated TGA (thermogravimetric analysis), heating at
5 8C per minute under nitrogen also confirmed this new salt
decomposed via a complex condensation process, releasing
a series of cyclic dimethylsiloxanes (D3 through to D12) and po-
tassium oxide. This is shown in Scheme 4.
Analysis of all the data suggested the salt exists as a dimer-
ised complex with one molecule of hydrogen bonded water of
hydration, as shown in Figure 5.
Scheme 4. Thermal decomposition of dipotassium dimethylsilanediolate
monohydrate salt.
Figure 5. Proposed structure of dipotassium dimethylsilanediolate monohy-
drate salt.
This new dipotassium dimethylsilanediolate monohydrate
salt was patented by Dow Corning in US 5,969,173 in October
1999, and complimentary European and Japanese patents
were filed, with Dr. Clarke and co-inventors receiving a Dow
Corning Award in Midland, Michigan in 2000, for this achieve-
ment.
This new dipotassium dimethylsilanediolate monohydrate
salt was used as a monomer for the synthesis of siloxane co-
polymers, using a novel liquid/solid interfacial polymerisation
procedure. This invention was patented by Dow Corning in US
6,046,293, in April 2000, along with complimentary European
and Japanese patents. In this dual solid/liquid phase interfacial
reaction the solid dipotassium dimethylsilanediolate, was dis-
persed, but not dissolved, in a solution of dichlorodiphenylsi-
lane dissolved in anhydrous hexane. It was hoped that the re-
action might lead to alternating copolymers, with one unit
consisting of the dimethylsiloxy moiety, and the other the di-
phenylsiloxy moiety. However, the potassium silanolate end-
groups and bound water of hydration, lead to the formation of
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a random copolymer, but still retaining a 1:1 molar ratio of the
two feed monomers.[25–27]
(3) Synthesis of anhydrous dialkali dimethylsilanediolate
and siloxane copolymers
Dimethyl and diphenylsilanediolates[28] were shown to have
potential to be intermediates in the interfacial polymerisation
of dimethyl and diphenyl-siloxane polymers. Whilst the dipo-
tassium dimethylsilanediolate monohydrate salt could be used
to prepare copolymers, these had a random structure and
there was concern the single water molecule of hydration,
might be the cause of this randomisation, and other unwanted
side reactions.
Therefore, some outstanding work was conducted to pro-
duce, for the first time, a series of new anhydrous dimethyl
and diphenylsilanediolates (R2Si(OM)2), where R = Me or Ph,
and M = Li, Na and K were synthesised by the reaction be-
tween dimethyl and diphenylsilanediol and a metal or metal
hydride (M/MH where M = Li, Na and K). The anhydrous silane-
diolates were characterised by 29Si, 13C and 1H NMR, FTIR and
mass spectroscopy.
The general reaction Scheme for making anhydrous dialkali
organosilanolates is shown in Scheme 5.
Scheme 5. Synthesis for making anhydrous dialkali organisilanolates.
The following five disilanolates were successfully prepared,
using dimethylsilanediol, synthesised internally, with diphenyl-
silanediol, being obtained from a commercial supplier:
-Dilithiumdimethylsilanediolate—dimethylsilanediol and lithi-
um hydride in dry THF under N2
-Disodiumdimethylsilanediolate—dimethylsilanediol and
sodium hydride in dry THF under N2
-Dipotassiumdimethylsilanediolate—dimethylsilanedioland
sodium metal in dry THF under N2
-Disodiumdiphenylsilanediolate—diphenylsilanediol and
sodium amide in dry toluene under N2
-Dipotassiumdimethylsilanediolate—dimethylsilanedioland po-
tassium metal in dry THF under N2
It was hoped these anhydrous dialkali silanolate salts would
prepare alternating siloxane copolymers, using a solid/liquid
phase interfacial reaction procedure. The solid dialkali dime-
thylsilanediolate, was dispersed, but not dissolved, in a solution
of an appropriate dichlororganosilane (either dichlorodiphenyl-
silane or dichlorodimethylsilane) dissolved in anhydrous
hexane.
Whilst all five disilanolate monomers readily reacted to pro-
duce copolymers of equal monomer stoichiometry, the copoly-
mer was again not strictly alternating. 29Si NMR was used to
identify the copolymers produced were random, in nature,
confirming the silanolate end-groups on these new anhydrous
1129 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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disilanolate monomers, also created considerable scrambling

of the copolymer backbone structure, despite moisture being
absent.

(4) New synthesis procedures for the preparation of alter-

nating siloxane copolymers and alternating siloxane cyclic
monomers
An exciting “one-pot” synthetic route[29, 30] was developed for
preparing 1,1,5,5-tetramethyl-3,3,7,7-tetraphenylcyclotetrasilox-
ane and strictly alternating poly(dimethylsiloxanealt-diphenylsi-
loxane) copolymer. The synthetic route used the heterofunc-
Figure 6. 29Si NMR of 1,1,5,5-tetramethyl-3,3,7,7-tetraphenylcyclotetrasilox-
tional polycondensation of diphenylsilanediol and dichlorodi-
ane.
methylsilane in the presence of triethylamine, to prepare the
alternating cyclic siloxane and diethylamine, to prepare the al-
ternating copolymer. The cyclic siloxaneproducts were charac-
terized by single-crystal X-ray diffraction, 1H, 13C and 29Si NMR
spectroscopy, thermogravimetric analysis and differential scan-
ning calorimetry, this being expertise resident in the research
teams managed by Matisons and Clarke.][31–36]
1,5-Di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenylcyclote-
trasiloxane, alternating cyclic siloxane monomer, was also syn-
thesised by this novel synthetic route.[37]
The reaction scheme to prepare the crystalline alternating
cyclic siloxane monomer is shown in Scheme 6, below:
Figure 6 and Figure 7 show 29Si NMR and single-crystal XRD
image of 1,1,5,5-tetramethyl-3,3,7,7-tetraphenylcyclotetrasilox-
ane.
Scheme 7 shows the preparation of a medium viscosity, high Figure 7. Single-crystal XRD image of 1,1,5,5-tetramethyl-3,3,7,7-tetraphenyl-
molecular weight, dimethylsiloxy–diphenylsiloxy alternating cyclotetrasiloxan.
co-polymer, obtaining a 75 % yield.[29, 30] Advanced modulated
DSC (differential scanning) and other thermal analysis tech- This “one-pot” synthetic route for the preparation of pol-
niques, used by the Matisons and Clarke teams[31–36] were used y(DMS-alt DPS ) copolymer (Scheme 7) and its cyclic counter-
to show this polymeric oil had a mid-point glass transition (Tg) part (Scheme 6) is novel.
of @21.5 8C. GPC (gel permeation chromatography) was used Both schemes achieve 50 % of the phenyl group, on a 1:1
to show this oily alternating siloxane copolymer, uniquely had molar basis, arranged alternatively in in the PDMS back-bone.
a number average molecular weight (Mn ) of 61,763 and This result is impossible to achieve by blending polydimethyl-
a weight average molecular weight (Mw ) of 81,817 and a poly- siloxane and polydiphenylsiloxane or by conventional acid- or
dispersity (PD) of 1.42. base-catalysed ring-opening polymerisation (ROP) of octame-

Scheme 6. One-pot synthesis for preparing 1,1,5,5-tetramethyl-3,3,7,7-tetraphenylcyclotetrasiloxane.

Scheme 7. One-pot synthesis of a medium viscosity, high molecular weight, dimethylsiloxy–diphenylsiloxy alternating co-polymer.

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thylcyclotetrasiloxane (D4) and octaphenylcyclotetrasiloxane

D4Ph.[38–41]
In 1987, Babu and co-workers were the first to successfully
synthesize poly(DMS-alt-DPS) copolymers using diphenylsilane-
diol and bis(ureido)silane. However, bis(ureido)silane is made
from highly toxic phenylisocyanate[42] The procedure devised
by Babu et al., although effective, used highly toxic, and ex-
pensive reagents. Unlike the simple “one-pot” procedure re-
ported in this manuscript (Scheme 7), the Babu procedure is
totally unsuitable for commercial synthetic application. The sili-
con NMR of this alternating silicone oil (Figure 8) displays two
separate peaks, with no evidence of coupling microstructure.

Figure 10. Comparative DSC of the alternating dimethysiloxane-diphenylsi-

loxane crystalline cyclic material and the oily linear silicone copolymer mate-
rial.

(5) Synthesis of alternating 1,5-di-(ethylphenyl)-1,5-dimeth-

yl-3,3,7,7-tetraphenylcyclo cyclic monomer

The first synthesis of 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-

tetraphenylcyclotetrasiloxane[37] was reported using a new
“One Pot” procedure a recently reported for the preparation of
Figure 8. 29Si NMR of poly(DMS-alt DPS ) copolymer oil. new strictly alternating cyclic silicone monomers. The reaction
for this reaction is shown in Scheme 8.
One peak is at @19.2 ppm corresponding to polymeric dime-
thylsiloxane and another is at @47.9 ppm corresponding to the
diphenylsiloxane moiety, confirming that the copolymer is
structurally alternating in nature. Pleasingly, this data was also
in complete agreement with the results of poly(DMS-alt-DPS)
copolymer synthesis, earlier obtained by Babu.[42] Below is
shown comparative TGA data (Figure 9) and DSC data
(Figure 10) of the alternating dimethysiloxane–diphenylsilox-
ane crystalline cyclic material, and the oily linear silicone copo-
lymer material. Similarly, TGA data identified the higher tem-
perature stability of the linear co-polymer.

Scheme 8. One-pot synthesis of 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7tet-

raphenylcyclotetrasiloxane.

29
Si NMR, single-crystal XRD, TGA and DSC data is shown
below for this compound in Figures 11, 12, 13 and 14, respec-
tively.

(6) Hydrolylation modeling

Figure 9. Comparative TGA of the alternating dimethysiloxane-diphenylsilox-
ane crystalline cyclic material, and the oily linear silicone copolymer materi-
al.
Dr. Tony Aitchison in collaboration with Dr. Pamela Pasetto,
from the Universit8 du Maine, Le Mans, France, while co-super-
vising, along with the author, Master’s degree student Ms
Gaelle Leveque conducted modelling research investigating

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Figure 11. 29Si NMR of 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenyl-
cyclotetrasiloxane.
Figure 12. Single-crystal XRD data for 1,5-di-(ethylphenyl)-1,5-dimethyl-
3,3,7,7-tetraphenylcyclotetrasiloxane.
Figure 13. TGA of 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenylcyclo-
tetrasiloxane.
the hydrosilylation reaction between a silicon hydride and vari-
ous double bond structural moieties were investigated for
their completeness.[43, 44] Three variations were used in this
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Figure 14. DSC for 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenylcyclo-
tetrasiloxane.
study; polylactic acid with terminal double bonds, allyl soyate
which was a fatty acid derivative from soybeans with terminal
and internal double bonds, and polyisoprene with terminal
double bonds and methylated internal double bonds; see
Figure 15 for unsaturated moieties investigated in this re-
search.
Figure 15. Examples of the various double bonds tested in the system.
1,1,3,3-Tetratmethyldisiloxane was used as the as the silicon
hydride model reagent. Catalysts such as Speier’s catalyst
(50 ppm), PtO2 and Karstedt’s catalyst (5 ppm) were used. Of
the three catalysts investigated and analysed by 1H NMR after
two hours of reaction, found Karstedt’s catalyst to be the best
catalyst for this system. The efficiency of the system was deter-
mined by the loss of chemical shifts in the 1H NMR at 4.6 ppm
for silicon hydride and the corresponding double bond group.
The researchers claim that hydosilylation of various hydrido
silicon molecules with acrylic functionalised natural rubber can
result in various materials, as outlined in Scheme 9, shown
below.
Foreseeable applications for these materials exist in the
areas of, but not limited to, degradable materials due to the
natural rubbers capability to degrade, medical applications
due to the silicon’s antimicrobial properties, and much more.
There has been some concern raised about the ability to
insert hydroalkoxysilanes to internal double bonds, using the
catalysts mentioned above. Generally, insertion only occurs to
terminal double bonds. Insertion to all double bonds has been
observed when chlorosilanes silanes have been used. There-
fore, further research may be required to validate the out-
comes, reported.[45]
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Scheme 9. Hydrosilylation between a silicon hydride and various double bond structural moieties
(7) Silicon modified electrolytes for Li ion batteries, in part-
nership with Michigan State University
Dr. Tony Aitchison spent twelve months on an American Aus-
tralian Association researcher exchange program, with informa-
tion provided from private correspondence with Dr. Tony
Aitchison[43] and conference presentations[46] being funded by
Dow Chemical, where he worked to modify modified electro-
lytes for Li ion batteries with silicon functionality. Organic elec-
trolytes have temperature useable range of @10 8C to + 60 8C.
Conventional organic ligands, coordinate with lithium ion
are shown in Figure 16.
Ethylene carbonate attached by the silylation reaction was
attached to various hydrido silicon compound, as shown in
Figure 17, and evaluated for improved lithium ion electrolyte
thermal properties.
Figure 16. Conventional organic ligands, coordinate with lithium ion
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Conductivity versus temperature, for these new electrolytes,
were assessed with the PDMS copolymer (PHMS-ECV) proving
to be the most effective, as shown in Figure 18. This work was
protected by two US Provisional patents.[47, 48]
(8) Ring opening polymerisation of silicone polymers
Fielden, Embery, Matisons and Clarke also reported fascinating
research using phosphoronitrile chloride for the Lewis acid cat-
alysed ring opening of silicone polymers[38]
Embery, Clarke and Matisons also provided two comprehen-
sive reviews, about the ring opening polymerisation of silicone
polymers.[39, 40]
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Figure 17. Silicon modified Li ion electrolytes.

TGA confirmed the POSS-PEG compounds improved in ther-

mal stability as the attached PEG molecular weight increased,
and similarly DSC showed an increasing glass transition (TG) as
the attached PEG molecular weight increased. This reflected

Figure 18. Conductivity of Si electrolytes.

Octafunctionalized Polyhedral Oligomeric Sil-

sesquioxanes (POSS)

(1) Pegalated POSS

A series of highly structured pegalated POSS (POSS-PEG) mole-
cules[49, 50] were synthesised then characterised with proton,
carbon and silicon NMR, TGA and DSC. First it was necessary to
synthesise a series of highly defined ethylene glycol monoeth-
ers, with repeat units 2, 3, 4 and 6 repeat units. The reaction
undertaken is shown in Scheme 10.
Octafunctional poly(ethylene glycol) (PEG) derivatives of two
different POSS structures: octa(dimethylsiloxy)silsesquioxane
(Q8M8H) and octa(hydrido)silsesquioxane (T8H), were prepared
with attached PEGs have varying chain lengths (n) from 2 to 6.
The synthesis procedure is shown in Scheme 11.

Scheme 11. Synthesis of two different POSS structures: octa(dimethylsiloxy)-

Scheme 10. First stage synthesis a series of highly defined ethylene glycol silsesquioxane (Q8M8H) and octa(hydrido)silsesquioxane (T8H), were prepared
monoethers, with repeat units 2, 3, 4 and 6 repeat units. with attached PEGs have varying chain lengths (n) from 2 to 6.

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the increasing thermal stability and boiling points of the at-
tached PEG moieties, as their molecular weight increased.
WAXD studies showed that the homologous series of PEG-
modified POSS materials were amorphous, although there was
some presence of small disordered regions of POSS crystals, in
contrast to neat POSS, which is highly crystalline. Rheological
characterization indicated Newtonian behaviour for POSS-PEG
with the viscosity of POSS-PEG material changing with increas-
ing PEG molecular weight. Activation energies of the hybrids
were also found to be higher than for the neat PEG due to the
bulky POSS unit and decreased as its concentration reduced
with increasing molecular weight, which is opposite to the in-
fluence of degree of polymerization on the activation energy
of neat PEG flow.
(2) POSS-Methyl Methacrylate-Based Cross-Linked Hybrid
Materials
The PEH modified—octa(dimethylsiloxy)silsesquioxane (Q8M8H)
series of molecules shown in Scheme 11, were further function-
alized by reaction with methacryloyl chloride to prepare
POSS—acrylic cross-linker materials.[51]
These cross-linkers were then combined with methyl metha-
crylate monomer and crosslinked with benzoyl peroxide initia-
tor to produce a series of hybrid materials (see Scheme 12).
The amounts of POSS—cross-linker, combined with methyl
methacrylate monomer ranged from 0.1 to 0.5 mol %. Thermal
investigations these materials were conducted using TGA and
Scheme 12. Synthesis of POSS-methyl methacrylate-based cross-linked
hybrid materials.
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DSC, revealing that both POSS concentrations and PEG chain
length play important roles in defining structure-property rela-
tionships. Incorporation of POSS always increased thermal sta-
bility. Although the POSS is a bulky and multifunctional cross-
linker, glass transitions did not always increase. In some cases,
bulkiness of the group created additional free volume and
chain separation, which led to a reduction in the glass transi-
tion temperature.
(3) POSS- Polyurethane Cross-Linked Hybrid Materials
A series of polyurethane hybrid networks were synthesized
using octakis(m-isoprenyl-a,a’-dimethylbenzylisocyanato dime-
thylsiloxy) octasilsesquioxane (Q8M8TMI). This POSS-TMI com-
pound was used as a crosslinking agent, for series of commer-
cially available polyethethylene glycols, using dibutyltin dilau-
rate as catalyst, to produce a series of inorganic-organic cross-
linked polyurethane materials.[52, 53] The polyethylene glycols
crosslinked had the following nominal weight average molecu-
lar weights (Mw ) @600, 1000, 2000, 4600, 8000, and 10 000. The
hybrid polymers produced ranged from a soft rubber that was
flexible but had poor tear strength for the 600 g mol@1 polyeth-
ylene glycol up to a tough rubbery sheet for 2000 g mol@1
polyethylene glycol, finally becoming a hard, waxy white solid
for 10 000 g mol@1 polyethylene glycol.
The formation of the urethane linkages within polyurethane
hybrids was confirmed by photoacoustic FTIR spectroscopy.
Scheme 13. Synthesis of POSS–polyurethane cross-linked hybrid materials.
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TGA and DSC studies demonstrated that the incorporation of
the POSS crosslinking agents, which altered the thermal prop-
erties of the polyurethanes, and that this was dependent on
the length of the polyethylene glycol chain.
The synthesis of octakis(m-isoprenyl-a,a’-dimethylbenzyliso-
cyanato dimethylsiloxy) octasilsesquioxane (Q8M8TMI) is shown
in Scheme 13.
(4) Synthesis and Liquid Crystalline Properties of Octa(ami-
no-nitro-azobenzene) silsesquioxanes (unpublished re-
search)
Dr. Kristina Constantopoulos conducted some outstanding
POSS functionalisation research, whilst undertaking a PhD at
Flinders University. A brief overview of outcomes from this
work is provided below from private correspondence with Dr.
Kristina Constantopoulos[54] and from a series of conference
presentations.[55–61]
Octa(dimethylsilyloxy)silsesquioxane cages containing dipo-
lar, amino nitro-azobenzene species (POSS-LCs) were devel-
oped, with the investigation of t synthetic pathways. A conver-
gent-type route was found to lead to penta-substituted com-
Scheme 14. Synthesis and liquid crystalline properties of octa(amino-nitro-azobenzene) silsesquioxanes.
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pounds, whereas a divergent-type pathway gave the desired
fully reacted octa-functionalized materials. Hydrosilylation of
an N-alkenyl-N-methylaniline species with Q8M8H, followed by
a post diazonium coupling of 4-nitrobenzenediazonium tetra-
fluoroborate salt with the POSS-aniline core. The products
were chemically characterized by various proton, carbon and
silicon nuclear magnetic resonance (NMR) spectroscopies and
elemental analysis. The properties of the POSS-LCs were deter-
mined using differential scanning calorimetry (DSC), polarized
optical microscopy (POM) and X-ray scattering analysis. Opti-
mal microscopy of the POSS-LC supermolecules showed a tex-
ture consisting of elongated b.tonnets, indicating the pres-
ence of a Smectic A mesophase. A new liquid crystalline azo-
benzene silsesquioxane has thus been synthesized, which
holds promise as a material with enhanced switching proper-
ties due to the reduced chromophore packing density provid-
ed by the bulky silsesquioxane nanocage scaffold, to which
they are covalently attached. Scheme 14 is shown below for
the synthesis of octa functionalised POSS-LC. The pentafunc-
tionalised reaction, although successful is not detailed in this
manuscript, as it seemed to have less value.
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(5) Specialist POSS Materials and Water Treatments
A detailed understanding of polyhedral oligomeric silsesquiox-
ane (POSS) synthetic procedures, as identified above and at
conferences[62–65] were also applied to an investigation into the
use of cellulose acetate, reverse osmosis mixed–matrix mem-
branes (MMMs) which are an emerging technology involving
the incorporation of nanoparticles to improve the performance
of these membranes.
Aminoisobutyl POSS and isocyanante modified POSS were
incorporated into cellulose acetate reverse osmosis mem-
branes.[66] These MMMs were characterized and the per-
formance assessed. Scheme 15 shows an unmodified aminoiso-
butyl POSS and the isocyanate modified version of these nano-
materials.
Nanocomposite cellulose acetate reverse osmosis mem-
branes were cast with incorporation of 0.5, 1.0 or 5.0 weight %,
unmodified and isocyanate modified POSS. The isocyanate
modified POSS additive showed better dispersion than POSS,
seen in FTIR and XPS analysis. All modified cellulose acetate
membranes showed increased water flux relative to an un-
modified membrane, although the isocyanate modified POSS
displayed lower increase in flux compared to the unmodified
POSS.
Unfortunately, salt rejection was found to decrease signifi-
cantly with increasing POSS modification. Average salt rejec-
tion for the three, isocyanate modified POSS nanoparticles re-
duced from 39 % to an average of 15 %. The unmodified POSS
nanoparticles displayed much poorer average salt rejection of
6 %.
In general, it was observed as flux increased, salt rejection
increased, generally with increasing nanoparticle inclusion. The
unmodified POSS showed higher flux and lower salt rejection
compared to the isocyanate modified POSS.
Scheme 15. Aminoisobutyl POSS and isocyanante modified POSS were synthesized and then incorporated into cellulose acetate reverse osmosis membranes.
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Sol-Gel, Silicate, Geopolymer and Silane Tech-
nologies
(1) Silica-Encapsulated Dendrimer-Palladium Catalyst (un-
published research)
Mr. David Vincent conducted outstanding sol-gel research,
when at Flinders University, using a two-stage procedure to
stabilise palladium nanoparticles within a generation-3, hydrox-
yl-terminated polyamidoamine (G3-PAMAM-OH) dendrimer,
and then coated these nanoparticles with porous silica. The
following research is provided from private correspondence
with Mr. David Vincent[67] and conference papers.[68, 69]
UV-visible (UV-vis) spectroscopy showed that PdII ions
adsorb to amide nitrogen atoms within G3-PAMAM-OH den-
drimers and that the dendrimers optimally absorb palladium at
a PdII ion/PAMAM-OH ratio of 30/1 (mol mol@1). Attenuated
total reflectance Fourier transform infrared (ATR-FTIR) spectro-
scopic analysis of PdII-PAMAM-OH, Pd0-PAMAM-OH and aged
Pd0-PAMAM-OH solutions, suggested that PdII ions also co-ordi-
nated to amide carbonyl groups and that Pd0 nanoparticles do
not co-ordinate to internal amides. Transmission electron mi-
croscopy (TEM) showed that stable and well-dispersed 2.5 nm
Pd0 nanoparticles form after the reduction of PdII ions and UV-
vis and ATR-FTIR suggested that these exist within the dendri-
mer interior. Diffuse reflectance Infrared Fourier transform
(DRIFT) spectroscopy and X-ray photoelectron spectroscopy
(XPS) analysis showed that Pd-PAMAM-OH dendrimers were
entirely encapsulated within a silica coating. Scanning electron
microscopy (SEM) indicated that the coated dendrimers con-
sisted of large clumps of 0.1 mm spherical aggregates of silica.
Thermal gravimetric analysis (TGA) showed that the silica ma-
terial was thermally stable to 135 8C.
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This new complex, composite material was found to be an

effective catalyst for the hydrogenation of alphamethylstyrene.
This silica material was easily recycled and able to be re-used
in at least six consecutive reactions, with only an initial drop in
the hydrogenation activity of the silica and control catalyst
was attributed to a loss of material through the pores of the
catalyst filters during the first filtration for re-use. Subsequent
activities stabilised and the silica catalyst was found to be
more catalytically-active than commercially-available palladium
on carbon.
The stabilization procedure for incorporating palladium
nanoparticles within hydroxyl-terminated polyamidoamine
(PAMAM-OH) dendrimers and their inclusion in a sol-gel proce-
dure to produce silica-coated Pd-PAMAM-OH dendrimers, is
Figure 20. UV-vis used to optimise the PdII/PAMAM-OH ratio in the dendri-
shown in Figure 19. mer complex.
The silica catalyst was then used in a series of hydrogenation
experiments to determine its activity and re-usability. It was
found that the material could be easily recycled and was
found to be more catalytically active than a corresponding Pd/
C control.
UV-vis analysis was used to optimise the PdII/PAMAM-OH
ratio in the dendrimer complex. Figure 20, verified the opti-
mum PdII concentration occured at a PdII/PAMAM-OH
mol mol@1 ratio of 30/1.
Figure 21 shows FTIR DRIFT analysis of these PdII/PAMAM-OH
nanoparticle catalyst particles, and clearly shows the porous sil-
icate coating on the exterior of these nanoparticles, stabilising
these materials from agglomeration and allowing the materials
to operate efficiently.
High-resolution SEM microscopy images in Figure 22 clearly
shows the porous structure of the silica coated PdII/PAMAM- Figure 21. FTIR DRIFT analysis of the PdII/PAMAM-OH nanoparticle catalyst
OH nanoparticle catalyst particles. This image clearly demon- particles
strates the porosity, of this material, interspersing the spherical
0.1 mm clumps of catalyst aggregates
Oxidation is qualitatively observed as a colour change from nanoparticle particles, after six hydrogenation experiments
black (Pd0) to orange (PdII) over time. Figure 23 shows four Pd- were conducted. It has been postulated that the fine material
PAMAM-OH samples, from left to right. (a) PdII-PAMAM-OH, has been washed away during the six recycling experiments,
freshly-reduced, (b) Pd0-PAMAM-OH, (c) 2 month old Pd0- and this accounts for a minor loss in catalytic activity with use.
PAMAM-OH and (d) 3 month old Pd0-PAMAM-OH solutions.
Lower resolution SEM microscopy images in Figures 24 clear- (2) Novel Grafting to Silica
ly shows the increased level of fine porous silica coated PdII/
A. Chemical Attachment of Porphryn to silica flour
PAMAM-OH nanoparticle particles, before hydrogenation ex-
periments were conducted. An aldehyde functionalised silane was chemically attached to
Lower resolution SEM microscopy in Figure 25 clearly shows silica powder, this being a versatile bridge to attach porphyrin
a reduced level of fine porous silica coated PdII/PAMAM-OH to the surface of silica.[70] The aldehyde functionality is ob-

Figure 19. The stabilization procedure for incorporating palladium nanoparticles within hydroxyl-terminated polyamidoamine (PAMAM-OH) dendrimers and
their inclusion into a sol-gel matrix

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Figure 22. High resolution SEM microscopy showing the porous structure of
the silica coated PdII/PAMAM-OH nanoparticle catalyst particles
Figure 23. Qualitative oxidation colour change from black (Pd0) to orange
(PdII) over time.
Figure 24. SEM microscopy showing increased fine porous silica coated PdII/
PAMAM-OH nanoparticle particles, before hydrogenation.
tained by a simple ozonolysis procedure of the surface-bound
allyl silane, where the double bonds are oxidized in high yield
to the desired aldehyde. Mono-amino porphyrin was attached
to the silica surface under mild conditions via Schiff-base link-
age.
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Figure 25. SEM microscopy showing a reduced level of fine porous silica
coated PdII/PAMAM-OH nanoparticle particles, after six hydrogenation ex-
periments conducted.
Commercially available allyl functionalised silica flour was
treated with ozone, to produce an ozonide, which was then re-
duced to the aldehyde. A Schiff-base reaction was then em-
ployed to chemically attach p-nitrotetraphenylporphyrin
(amino porphyrin) to the silica surface, as shown in Scheme 16.
Scheme 16. Synthesis of porphyrin functionality attached to silica particles.
FTIR DRIFT was used to verify conversion of the allyl func-
tionalised silica flour (Figure 26) to the aldehyde functionalised
silica (Figure 27), following ozonolysis and reduction with zinc
and acetic acid.
TGA analysis of the porphyrin functionalised silica flour con-
firmed the attached porphyrin degraded between 400 8C and
700 8C and the amount of porphyrin attached to the silica was
about 9.4 wt %.
B. Chemical Attachment of PMMA to silica flour
A surface-bound free radical initiator was used to chemically
attach novel PMMA brushes to a silica surface.[70] Anchored
PMMA was obtained by free radical initiation using a copper
mediated aldehyde/redox free radical polymerization proce-
dure, as shown in Scheme 17. FTIR and TGA data were used to
determine and characterize the attachment to the silica sur-
face.
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Scheme 18. The general hydrolysis and condensation chemistry of sol-gel re-
actions.

Figure 27. FTIR DRIFT used to verify conversion of the allyl functionalised
silica flour to the aldehyde.
and Improving Porous Sol-Gel Materials for Water Purifica-
tion”.[71–73] The research was conducted in partnership with the
National University of Singapore, Public Utilities Board (Singa-
pore), Deltares (Holland), and United Water (Australia).
Organosilicon sol-gel materials were developed for the treat-
ment and purification of run-off and storm-water, allowing un-
sightly concrete drains shown in Figure 28, considered to be
a major problem in Singapore, to be transformed into people
friendly waterways, as shown in Figure 29.

Figure 26. FTIR DRIFT of the allyl functionalised silica flour.

Figure 28. Unsightly concrete drains.

Scheme 17. Surface-bound free radical initiator was used to chemically

attach novel PMMA brushes to a silica surface.

Following water washing, TGA identified 7.5 % wt % PMMA

polymer was attached to the surface of silica, with thermal
degradation of the polymer occurring between 150 8C and
350 8C.

(3) Sol-Gel Materials for WSUD Water Treatment Applica-

tions
Australian Research Council (ARC) Linkage grant—LP0777033
funded a two-year WSUD water treatment project “Modifying Figure 29. People friendly waterway.

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Scheme 19. Acid catalyzed sol-gel hydrolysis.
Scheme 20. Base catalyzed sol-gel hydrolysis.
The general hydrolysis and condensation reactions for sol–
gel technologies shown below in Scheme 18
The hydrolysis reaction can be catalysed at low pH, known
as acid-catalysed hydrolysis, shown below in Scheme 19, or at
high pH, known as base-catalysed hydrolysis, shown in
Scheme 20.
Base-catalysed condensation reaction, perhaps the more
common procedure, involves the attack of a nucleophilic de-
protonated silanol on a neutral silicic acid (Scheme 21).[74]
Figure 30 shows Australian silicon researchers Dr. Kim
Nguyen and Dr. Elda Markovic, from Flinders University who
obtained “break-through” data at the newly constructed Singa-
pore-Delft Water Alliance laboratories at the University of Sin-
gapore.
This data was analysed by Deltares in Holland and results
are shown in Figure 31 (a, b, c, d and e)
(4) Silicate Encapsulation of a Chloride Salt Phase Change
Material for High Temperature Energy Storage
Encapsulated phase change materials (EPCMs) have been de-
veloped based on a molten eutectic salt of barium chloride
(53 wt %), potassium chloride (28 wt %) and sodium chloride
(19 wt %) for low cost EPCM storage systems. Unpublished re-
search conducted by Dr. Neil Trout with data provided by pri-
Scheme 21. Base catalyzed sol-gel condensation.
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vate correspondence[75] and a conference paper.[76] The latent
heat, melting point and thermal stability of the phase change
material (PCM) was determined by DSC and was found to be
in good agreement with results published in the literature. A
sodium silicate/fly-ash system was developed to encase the
molten salt, over the corrosive, high-temperature environ-
ments to which the system was to be subjected. The thermal
stability of the silicate shell formed a stable casing for the
chosen PCM at 200 8C and/or 600 8C. Figure 32 shows the
EPCMs after subjected to cycling temperatures up to 600 8C.
(5) Improved Curing of Sodium Silicate Solutions
Aqueous, alkaline sodium silicate solutions can be cured, via
the addition organic esters to produce a cross-linked “glass
like” water insoluble silicate materials, suitable for soil stabiliza-
tion. In basic media, these esters hydrolyse to produce organic
acids, and other side products, which in turn neutralise the al-
kalis in the aqueous sodium silicate solution. This results in the
precipitation of “glassy” silicate materials, which are hard and
water insoluble and can be used for stabilizing soil prior to
construction. The curing process is shown in Scheme 22. Un-
published research conducted by Dr. Neil Trout with data pro-
vided by private correspondence.[75]
Dr. Neil Trout investigated ester curing compounds and im-
proved the “wet strength” of cured sand-filled sodium silicate
solutions to an acceptable compressive strength of 2.6 :
0.2 MPa. The appearance of cured, unfilled sodium silicate is
shown in Figure 33. Figures 34 and 35 show sand filled sodium
silicate mortar, immediately prior to undergoing a compressive
strength test and the mortar after undergoing a compressive
strength test.
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Figure 30. Australian, silicon researchers, Dr. Kim Nguyen, and Dr. Elda Markovic, obtaining ‘break-through“ data at the newly constructed Singapore-Delft
Water Alliance laboratories at the University of Singapore.
Scheme 22. Aqueous alkaline sodium silicate solutions cured, using organic esters to
produce a cross-linked “glass like” water insoluble silicate for soil stabilization.
(6) Slump and Curing Investigation of Fly-Ash and Black
Sand Based Geopolymer Concrete
Most commonly used superplasticizers, in Portland cement
concretes have shown limited effect on the slump and worka-
bility of the fly-ash and fly ash-black sand blended silicate
based geopolymer concrete. This is believed to be due to the
high alkalinity and corrosive nature of GeoPolymer systems.
Unpublished rheological research conducted by Dr. Neil
Trout, with data provided by private correspondence, identi-
fied surfactants which improve the flow properties of GeoPoly-
mer slurries and mortars. These surfactant systems have not
been previously reported in the literature, nor have they been
used in industry, but could provide a pathway to improving
flow properties of GeoPolymer silicate concretes and mortars.
See Figure 36, demonstrating the use of a Brookfield viscome-
ter to test the viscosity of GeoPolymer slurries. See Figure 37
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below, showing a cured GeoPolymer silicate mortar.
Unpublished research conducted by Dr. Neil Trout
with data provided by private correspondence.[75]
(7) Sol–gel Aerogel filled foams for improved insu-
lation
Flexible, thermally insulating composites of isocya-
nate polymer foam and porous silica aerogel gran-
ules, which have improved thermal insulation prop-
erties compared with the pure foam, whilst retaining
flexibility properties of the foam were developed.
Unpublished research conducted by Dr. Lucas John-
son with data provided by private correspond-
ence.[77]
These new silica, sol-gel aerogel composite foams
have key insulation properties as follows:
A. Low density, flexible polyurethane—aerogel
composite foam was developed (Density- 55 kg m@3,
k value @35.8 mW m@1·K, closed cell content @40 %
by volume and cell diameter @0.1–1 mm)
B. Low density, low aerogel content polyisocyanurate (PIR)
rigid foam (Aerogel content @18.4 % v/v, density
@112.2 kg m@3, closed cell content @81 % by volume, and k
value @39.9 mW m@1·K)
C. High density, high aerogel content polyisocyanurate (PIR)
rigid foam (Aerogel content @92.5 % v/v and density
@292.7 kg m@3)
See images of the foam composites A, B and C in Fig-
ure 38 a, 38 b and 38 c, respectively.
(8) Silylation of Dantocol Bonding Agent in Polymer Bonded
Explosives
Cast-cured Polymer Bonded Explosives (PBXs) are often used
to achieving Insensitive Munitions (IM) compliance. Formula-
tions typically employ a bonding agent to improve adhesion
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Figure 32. Sodium silicate/fly-ash encapsulated phase change materials

(EPCMs) subjected to temperatures up to 600 oC.

Figure 33. Unfilled sodium silicate.

Figure 34. Testing mortar.

Figure 31. a) Breakthrough data for copper. b) Breakthrough data for arsen-
ic; c) Breakthrough data for lead. d) Breakthrough data for zinc. e) Break-
through data for chromium(III). Figure 35. Crushed mortar.

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Figure 36. GeoPolymer viscosity.
Figure 37. Cured GeoPolymer mortar.
between particulates and the binder system. A common bond-
ing agent for nitramine based composites is an hydantoin de-
rivative 1,3-bis(2-hydroxyethyl)-5,5-dimethylhydantoin, com-
mercially referred to as Dantocol.[78, 79]
Scheme 23. Polymerisation of a typical polymer binder system used in PBX materials.
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Figure 38. (A) Low density, flexible polyurethane—aerogel composite, (B)
Low density, low aerogel content polyisocyanurate (PIR) rigid foam and (C)
High density, high aerogel content polyisocyanurate (PIR) rigid foam.
This bonding agent has been used for many years to in-
crease interaction between filler and binder in cast-cured poly-
mer bonded explosives (PBXs) composites, however, the exact
mechanism by which this occurs has been poorly understood.
Without a bonding agent, the PBX system is susceptible to
dewetting, mechanical failure with reduced adhesion between
filler and binder, causing failure under stress.
Scheme 23 shows the polymerisation of a typical polymer
binder system used in PBX materials
Figure 39 shows the chemical structure of RDX nitramine ex-
plosive commonly employed in PBX materials, chemically
known by its IUPAC name of 1,3,5-trinitro-
perhydro-1,3,5-triazine or its common name
or its common name as cyclotrimethylene-
trinitramine. This just one of many explo-
sive fillers, used up to 80 % content in PBX
Figure 39. RDX.
materials. It is a hard, white, crystalline solid
that is ground into a fine white powder,
and is incredibly stable for an explosive that is generally only
sensitive to a percussive force.
As for many polymeric binder systems the inherent attrac-
tion between the polymeric binder and the filler can be im-
proved by a coupling agent, and for many years a small addi-
tion of 1,3-bis(2-hydroxyethyl)-5,5-dimethylhydantoin, commer-
cially known as Dantocol, improves the adhesion between the
binder and the filler, greatly improving tensile properties of
the rubbery, composite explosive, Figure 40 shows the fourfold
improvement in the tensile properties of a PBX material, with
and without Dantacol.
It had been postulated that polar bonding improved the ad-
hesion between the polar nitramine filler and non-polar binder
systems. The belief being that polar Dantocol molecules prefer-
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Scheme 24. Silylation the two hydroxy functional groups on 1,3-bis(2-hydroxyethyl)-5,5-dimethylhydantoin (Dantocol).
Figure 40. Fourfold improvement in the tensile properties of a PBX material,
with and without Dantacol.
entially adsorb to the polar nitramine filler via secondary bond-
ing, then a subsequent chemical reaction of hydroxy groups
Dantocol to the isocyanate functionality of the binder system
produced primary bonds to enhance interfacial adhesion and
tensile strength of the PBX.
Interestingly, although the benefit of using a Dantocol cou-
pling agent was well known, the precise mechanism, although
believed to be polar in nature, was never fully elucidated.
Therefore, in our work, a silylating agent was used to progres-
sively silylate the two hydroxy functional groups on the Danto-
col. The silyating chemistry employed is shown in Scheme 24.
DRIFT FTIR was used to monitor the change in the polar in-
teractions within the PBX, as this silylation process, progres-
sively reduced the ability of the Dantacol to undergo polar
coupling.
Figure 41 clearly demonstrates a progressive reduction in hy-
drogen bonding to RDX explosive as the level of silylation of
Dantacol hydroxy groups is increased.
Accommodating Gel—Intraocular Lens
Seeking an outcome with greater commercial impact Brien
Holden Vision Institute—BHVI (based at the University of New
South Wales—UNSW)[80] negotiated with the University of
South Australia (UniSA) for Dr. Clarke’s research team to trans-
fer to that University’s Mawson Institute, research centre. The
BHVI is known for its role in developing the long wearing, high
oxygen permeable, silicone hydrogel contact lens, patented in
1998 as US 5,760,100[12] The BHVI provided $2.25 AUD million,
in cash, over three years for Dr. Clarke’s team to take over all
synthetic silicone copolymer research for this AG-IOL Vision
CRC initiative. At the time, this was Australia’s largest academic
research project in silicon chemistry, with the team taking the
technology in an entirely new direction over three years con-
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Figure 41. FTIR showing a progressive reduction in hydrogen bonding to
RDX explosive as the level of silylation of Dantacol hydroxy groups is in-
creased.
tracted on this project. The result coming from this research
was the world’s first, commercially viable, AG-IOL technology,
patented and published in June 2016, as a world patent.[22]
Professor Jean-Marie Parel[81] from the University of
Miami’s—Bascom Palmer Eye Institute(BPEI) introduced and
popularised the Phaco-Ersatz accommodating gel (AG) IOL
concept, in conference papers, during 1981 and 1982[82] before
publishing this work in 1986[83] plus other manuscripts].[84–86]
The concept is widely accepted. Earlier work by others include
early theories about accommodation of the lens by Helm-
holtz[87, 88] Kessler[89–91] and Agarwal and associates.[92, 93]
Figure 42 shows the image of an eye suffering cataract
blindness, which Parel’s “Phaco-Ersatz” AG-IOL material could
be used to treat the condition.
Figure 43 shows a typical healthy eye, and most importantly
the lens, which can deteriorate with age, leading firstly to pres-
byopia and ultimately cataract blindness
Figure 44 demonstrates the effects of presbyopia, also asso-
ciated with cataract blindness, which alters the focus of light
Figure 42. Image of an eye suffering cataract blindness.
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Figure 43. Image of a healthy eye.
Figure 44. The effect of presbyopia, associated with cataract blindness, alter-
inng the focus of light through the eye, leading to blurry vision.
through the eye, leading to blurry vision when viewing near
images.
Parel discussed some research outcomes investigating Ersatz
silicone materials for his “Phaco-Ersatz” procedure. Reported
were room temperature vulcanised (RTV) silicone polymers and
two-part Low Temperature Vulcanised (LTV) silicones,[83, 94, 95]
Norbby[96] published a patent for injectable silicone polymers
for intraocular lens use[97] and published a patent for photo-
curable silicone gel IOL[98] Koopmans published his PhD
thesis[99–102] in 2006, investigating the “Phaco-Ersatz” procedure,
but focussing on epithelial cell proliferation following AG IOL
cataract surgery. Koopmans used a confidential two-part hy-
drosilylation platinum cured silicone polymer gel, assumed to
have been provided for his research by Norrby.[103]
Figure 45. Master Plot of UV cured, difunctional end-chain, cross-linked, linear polysiloxane AG-IOL material.
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Following Parel’s manuscripts, many research teams at-
tempted to produce a workable Phaco-Ersatz AG-IOL, but all
failed. Knowing of BHVI’s success, developing the world’s first
long-wearing, oxygen permeable, silicon-hydrogel contact lens,
Parel formed a partnership with BHVI in the 1990s.[104–106] BHVI
and BPEI worked with CSIRO for many years to develop a pa-
tented mid-refractive index silicone photocurable Ersatz mate-
rial,[107–109] which was published widely.[110–114] However, there
were perceived inherent problems with the technology. Know-
ing the expertise of Dr. Clarke’s research in silicon technologies
and UV polymerisation[115–120] BHVI (UNSW) turned to this team
to assess these apparent problems, which prevented commer-
cialisation of this type of AG-IOL technology. A summary of the
key features and the problems associated with this approach
are as follows:[107–114]
· Use of an acid catalysed (cationic) ring opening procedure, to
polymerise three cyclic siloxane monomers
· A disiloxane endblocker (hexamethyldisiloxane) was used to
control the number average molecular weight
· The linear backbone consisted of dimethylsiloxane (major),
methyl(propylphenyl)siloxane (refractive index modifier) and
methyl(propylmethacrylate)siloxane (side-chain crosslinker)
· A photoinitiator used to crosslink (cure) the propylmethacry-
late group by ultraviolet (UV) light
This concept was interesting, but had practical limitations,
preventing commercial use, these being:
· High solvent leachables (80 % to 100 %) suggesting inade-
quate cure, after UV irradiation,
· Perceived cloudiness issues from UV initiator residues
· IOLs must contain UV stabilizers to protect the retina
from sun damage, which could prevent UV curing.
A “Master Plot” to simultaneously analyse extractables (%),
pre-cure viscosity (Pa s) and post cured shear modulus (kPa)
versus weight average molecular weight (Mw), of early linear
UV cross-linked silicone polymers was conducted. This Master
plot is shown in Figure 45.
Important KPIs (Key Performance Indicators) for a successful
AG-IOl include (a) low solvent extractable (leachable) material
ideally be less than 1 %, or if greater than 1 %, having a poly-
meric molecular weight greater than 1000; (b) a pre-cured vis-
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cosity below 12 Pa s; and (c) a post cured shear modulus less
than 2 kPa.
Analysis of the Master Plot, of a UV cured linear PDMS,
having a side-chain cross-linking system, clearly showed that it
was not possible for a linear PDMS polymer to have a high
enough polymeric molecular weight to provide a sufficiently
low post-cured modulus, and yet also retain a low enough
liquid viscosity to be injected through a syringe and have low
post-cured leachables.
Early Phase 1 animal trials by Professor Parel at BPEI with
this silicone side-chain UV cured AG IOL required the animals
to be prematurely euthanized, within 24 hours of surgery. This
was due to complications resulting from insufficient curing of
this material in the eyes of the rabbits used to test this materi-
al.
Two key findings also came from this Master plot study
1) To achieve low extractables it was found crosslinking func-
tionality needed to be attached to the end of each polymer
chain, and not along the side of the chains. End chain cross-
linking functionalization ensured every polymer chain would
be incorporated into the soft gel structure of the polymer,
thus minimising solvent leaching. With side chain crosslinking,
the cross-linking density was so light that many chains, espe-
cially the lower molecular weight chains had insufficient cross-
linking density to cure, leading to high, levels of uncured poly-
mer and high leachables. End-chain crosslinking overcame this
dilemma.
2) It was also found that was impossible to produce a linear
PDMS polymer with an end-curing system that met the strict
uncured viscosity, no more than 12 Pa s, and a cured shear
modulus of no more than 2 kPa, even though very low leacha-
bles results were obtained by this new end-chain curing
system.
Given the constraints above, a new, approach was em-
ployed. A two-step approach was employed, to develop
a novel tristar siloxane copolymer end chain, moisture curing
macromer. It is known that star shaped polymers have lower
uncured viscosities, at higher molecular weights, which can in
turn provide lower cured shear moduli at higher polymer mo-
lecular weights. To this end, three-armed PDMS silicone star
Figure 46. Moisture curing, functionalised polysiloxane trismacromonomer belnded with a moisture curing a,w-diacetoxymethyl terminated PDMS polymer
(DMS-D33 from Gelest).
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molecules (trismacromonomers) were synthesised. Model
PDMS variants were initially prepared. Two ensure complete re-
action a slight stoichiometric excess of PDMS polymer to the
three core functional groups was used. Two commercially
available a,w-dihydrido end-terminated linear PDMS prepoly-
mers, were trialed, having polymer molar attachment ratios
ranging from (3.1 to 3.6) : 1 to the trisvinylsilane core. The tris-
vinylsilane core used was tris(vinyldimethylsiloxy)phenylsilane
(TVDPS 95 %) CAS 60111-47-9 obtained from Gelest Inc., Morris-
ville, PA, USA.
A. PDMs Based Tristar Macromonomer as a “Model” AG-IOL
Material
The first step involved synthesising the moisture curing, low
refractive index, “model” PDMS tristar macromonomer. This
was achieved using readily available commercial siloxane co-
polymers terminated each end with hydride functionalisation.
Hydrosilyation was used to attach one of the two, hydride
ends of the PDMS polymer to the trivinylsilane core to produce
the three tristar PDMS macromonomers. To the remaining
three, hydride endgroups of the macromonomer. Hydrosilyla-
tion was used to attach three different moisture curing moiet-
ies, these being.
Silyl trimethoxy end-groups, by addition of trimethoxyvinylsi-
lane
Silyl diethoxy end-groups, by addition of diethoxymethylvi-
nylsilane
Silyl monoacetoxy end-groups (by addition of vinyldimethy-
lacetoxysilane
These, three moisture curing, functionalised trismacromono-
mers were very slow, taking days and sometimes weeks to
cure in a 35 8C oven at 100 % humidity. Curing was found to
significantly increase by blending with an a,w-diacetoxymethyl
terminated PDMS polymer. The a,w-diacetoxymethyl terminat-
ed PDMS polymer used was DMS-D33 (CAS 158465-54-4) from
Gelest Inc., Morrisville, PA, USA). Initial gelation occurred in an
hour or so, with complete gelation occurring in 1 to 2 days.
Figure 46 shows a Master Plot of one such blend. This tris-
macromonomer for this blend was prepared using a 3.2:1 stoi-
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chiometric ratio of a,w-dihydrido PDMS (DMS-H25, having vis-
cosity @500 cp and molecular weight @17 200 from Gelest
Inc., Morrisville, PA, USA) hydrosilyated chemically to a TVDPS
core.
Vinyldimethylacetoxysilane was added in slight excess,
under nitrogen at 70 8C using an hydrosilylation reaction (Kar-
stetd’s catalyst), adding to the three remaining hydrido groups
on the macromonomer. 1H NMR was used to confirm the dis-
appearance of Si@H peaks at 4.7 ppm and completion of the
reaction, thus producing a monoacetoxy terminated, moisture
curing trismacromonomer. This moisture curing trismacromo-
nomer was then blended with an a,w-diacetoxymethyl termi-
nated PDMS polymer (DMS-D33 (CAS 158465-54-4) from Gelest
Inc., Morrisville, PA, USA) having a nominal viscosity of 2000–
4000 cP and a molecular weight of 36 000.
Figure 46 clearly demonstrates there was an optimum blend
ratio of a,w-diacetoxy terminated linear PDMS polymer to
functionalised trismacromonomer of around 30 to 50 %. The
Master Plot shown in Figure 46 demonstrates that a minimum
of 50 % diacetoxy PDMS polymer (DMS-D33) is required in the
blend to achieve full cure, represented by a relatively low sol-
vent extractables of about 6 %. Similarly the uncured viscosity
of the blend of around 8 Pa s is well below the maximum spec-
ification of 12 Pa s, and the cured Shear Modulus after cure of
around 3 kPa is approaching the post-cure shear modulus
specification of 2 kPa.
Based on the blend results, above, preparation of a 50:50
blend of DMS-D33 (a,w-diacetoxymethyl terminated PDMS)
and diethoxy terminated trismacromonomer (synthesised by
hydrosilylation of diethoxymethylvinylsilane, using a 1:3.6
TVDPS to DMS-H31 hydride terminated star trismacromono-
mer) was tested for Phase 1 implant trials in the lenses of New
Zealand white rabbits at Bascom Palmer Eye Institute (BPEI), at
the University of Miami. The surgical procedure was undertak-
en, at the BPEI facility, by Dr. Esdras Arrieta, and overseen by
Professor Parel. The implantation surgery was completely suc-
cessful with all rabbits, for the first time, surviving an AG IOL
“Phaco- Ersatz” procedure for several months, without issue,
until the scheduled euthanasia time for removal of the lenses.
These lenses were sent to BHVI laboratories for evaluation. An
image of an explanted rabbit lens is shown in Figure 47.
Figure 47. Photograph of an explanted moisture curing, PDMS based AG-
IOL rabbit lens.
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B. One Pot, Mid-Index, Moisture Curing Tristar Macromono-
mer AG-IOL Material
The second step used base catalysed ring-opening polymeri-
sation to produce a specialist, moisture curing, mid-refractive
index, star polymer based on the simpler ‘model“ tristar macro-
monomer system. An a,w-divinyl terminated mid-index meth-
ylphenylsiloxy-PDMS copolymer prepared by anionic equilibri-
um polymerisation was used to attach one end of the a dihy-
dride terminated PDMS polymer, or copolymer to a trivinylsi-
lane core, to produce a hydride terminated, star siloxane mac-
romonomer.
Attempted Cationic (Acid) Ring Opening Polymerisation
(ROP) of Prepolymer
A considerable amount of research was undertaken using cat-
ionic (acid) ring opening polymerisation of octamethylcyclote-
trasiloxane and tetramethyltetraphenylcyclosiloxane with tetra-
methyldisiloxane as the end-blocker to produce a one-pot
moisture curing, mid-index silicon AG-IOL. The purpose being
to produce an a,w-dihydrido terminated mid-index methylphe-
nylsiloxy-PDMS copolymer as a prepolymer, similar, to the
PDMS ‘model“ moisture cured system studied above. The in-
tention was to prepare a diacetoxy functionalized, moisture
curing, trismacromonomer, thus avoiding blending with
a linear, a,w-diacetoxymethyl terminated siloxane copolymer.
However significant difficulties were encountered with the acid
catalyzed co-polymerisation reaction. Low conversion rates
and poor uptake of the tetramethyltetraphenylcyclosiloxane
were encountered making this synthetic route unviable.
Successful Anionic (Base) Ring Opening Polymerisation
(ROP) of Prepolymer
To overcome polymerisation issues with the cationic catalysed
system, it was decided to investigate an anionic catalysed ROP
procedure, using octamethylcyclotetrasiloxane (commonly D4),
2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS
77-63-3 from Sigma–Aldrich, which was a mixture of D3 and
D4Ph. In this process 1,3-divinyl-1,1,3,3-tetramethyldisiloxane
(CAS 2627-95-4 from Sigma–Aldrich, was used as an ‘end-stop-
per“ to control molecular weight. A complex washing and
drying process was employed as identified in [22]. The poly-
mer obtained was analysed by NMR, GPC, rheometer and re-
fractometry, having a molecular weight profile of Mn: 9940, Mw:
20 203, Mw/Mn : 2.03 and a low molecular weight peak of 8.6 %),
a refractive index (RI) of 1.438 and a Viscosity of 2.752 Pa.s.
Synthesis of the first successful one-pot moisture curing,
mid-index silicon AG-IOL
A “one-pot” procedure was developed to synthesise a diacetoxy
terminated mid-refractive index tristar siloxane copolymer. The
vinyl terminated methylphenyl-PDMS copolymer, synthesised
by anionic ROP was added, by hydrosilylation, to a phenyltris(-
dimethylsiloxy)silane core in a molar ratio of 3.6:1 (mol), using
1148 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Community Report

Karstedt’s (platinum) catalyst. Progress of the hydrosilylation

Table 1. Properties required for a successful polysiloxane based, accom-
reaction was monitored by 1H NMR. The disappearance of the modating gel – intraocular lens
Si@H bond from phenyltris(dimethylsiloxy)silane core indicated
that the hydrosilylation had gone to completion. Diacetoxyme- Property Targeted Target Outcome
thylsilane (in double excess) was then added to this same reac- Clarity Optically Clear Optically Clear
tion mix, in a second step, and stirred overnight. Disappear- Cure Approx. 24 hours 24 hours
Viscosity [Pa s] < 12 Pa s 1.2 Pa s
ance of the double bond shift confirmed the completion of
Refractive Index 1.435–1.44 1.439
the second hydrosilylation. A complex clean-up process was Density [g mL@1] > 1.0 g mL@1 1.02 g mL@1
employed as identified in.[22] The product was obtained as Shear Modulus [kPa] < 2 kPa 1.7 kPa
a clear viscous liquid, and stored under dry anhydrous condi- Solvent leachables [%] < 1 % ideally 27 %
tions before use. Properties of branched acetoxy mid index
polymer are as follows. Viscosity (7 days—anhydrous)
@4.37 Pa s; Three day cure in simulator—clear, cohesive gel; copolymer reducing the base catalyst (KOH) and increasing the
Refractive Index @1.439; Density > 1.000, GPC Mn @18 499; washing procedure with methanol to 12 times, reducing cyclics
GPC Mw @120 781; GPC Mp @31 231; GPC Polydispersity to less than 1 %. 1H NMR and GPC were used to confirm that
@6.529; and GPC Cyclics @7.79 % all cyclic siloxane species had been removed by this purifica-
tion process. “Crystal Clear” diacetoxy functionalised macromo-
nomer The product was prepared as previously,[22] to prepare
Second Phase 1 New Zealand Rabbit Implant Trial of one- a colourless and transparent macromonomer that did not
pot moisture curing, mid-index silicon AG IOL—at BPEI demonstrate haze in the eye. Key characteristics of this poly-
A second Phase 1 surgical procedure was undertaken, at BPEI mer are; Mn : 14 458; Mw: 55 135; Mw/Mn : 3.2; RI: 1.439; specific
(University of Miami). The implantation surgery was a complete gravity: 1.02; viscosity: 1.188 Pa s.
success with all rabbits, surviving an AG IOL procedure for sev- A summary of the properties of the “Crystal Clear”[22] AG IOL
eral months, until scheduled euthanasia and removal of the is shown below in Table 1:
lenses. These lenses were sent back to Australia for evaluation. A third series of Phase 1 surgeries, using New Zealand white
The image of a live New Zealand rabbit eye, after implantation rabbits were conducted at BPEI with these surgeries reported
of the AG IOL lens is shown in Figure 48. to be the most successful to date. The material was not toxic
to the rabbit eyes and provided crystal clear lenses, such that
the retina of treated rabbits could be clearly visualized for the
first time.
An image of the “Crystal Clear” AG-IOL cured, and continu-
ously immersed under balanced saline solution (BSS), displayed
complete transparency, even after 13 days of immersion in BSS
(ee Figure 49).

Figure 48. First successful explanted rabbit trials for a one-pot, moisture
curing, mid-index polysiloxane AG-IOL.

Haze Formation in the one-pot moisture curing, mid-index

silicon AG IOL
It was observed, unlike low refractive index, PDMS based,
moisture curing ‘model“ system first trialed at BPEI the mid-
index single pack moisture curing system could randomly de-
Figure 49. First ‘Crystal Clear’ explanted rabbit trials for a one-pot, moisture
velop cloudiness/haziness to varying degrees for different
curing, mid-index polysiloxane AG-IOL.
batches of material produced. Two contributions were identi-
fied:
· Permanent haze—resulting from inclusion of low molecular
Conclusions
weight siloxane cyclics in the polymer
· Temporary haze—resulting from the temporary presence A broad range of silicon chemistry has been undertaken in
of acetic acid from the curing process Australia, commercially since the mid-1960s with the establish-
Synthesis of the first “Crystal Clear” one-pot moisture curing, ment of Dow Corning and more recently by academic re-
mid-index silicon AG IOL searchers in the 1980s. Areas of silicon chemistry of greatest in-
The synthetic procedure was modified, to prevent haze for- terest include high-quality silicon metal production, polysil-
mation. The a,w-divinyl terminated mid-index PDMS-co-PMPS oxane polymers and copolymers, siloxane polymer emulsions

Chem. Asian J. 2017, 12, 1123 – 1152 www.chemasianj.org 1149 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

and microemulstions, siloxane cyclic synthesis, silane chemistry
and silane coupling agents, sol-gel silicon technologies, porous
silicon, siloxane polymer degradation mechanisms, silicon hy-
drogel contact lenses, silanolate and disilanolate synthesis, si-
loxane interfacial polymerisation, hydrosilylation siloxane-
rubber composite materials, silicon electrolytes for lithium ion
batteries, silicon chemistry to better understand PBX materials,
octafunctionalized polyhedral oligomeric silsesquioxanes
(POSS) synthesis, POSS hybrid materials, sol-gel encapsulated
hydrogenation catalysts, chemical and polymer modification of
silica, silicon sol-gel water treatment materials, silicate sol-gel
phase change energy storage materials, aqueous silicate soil
grout stabilisation, silicate fly-ash based GeoPolymer concretes
and mortars, sol-gel aerogel insulating foams, “Phaco-Ersatz”
Accommodating Gel—Intraocular Lens technologies.
Acknowledgements
The authors thank Dr. Richard Grant, Dr. Kristina Constantopou-
los, Dr. Tony Aitchison, Dr. Chris Embery, Dr. Lee Hoffman, Dr.
Andrew Schamschurin, Peter Folland, Sean Steed, The late F. W.
Gordon Fearon, Prof. Stephen Clarson, Dr. Mark Fisher, Dr.
Jason Watling, Dr. Paul Erickson, Andrew Keough, and Dr.
Lucas Johnson.
Keywords: Asia · Australia · chemistry · silicon · technology
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