Chemistry New Boundaries 2016 by University of Southampton

Chemistry New Boundaries

Materials innovation Unlocking the potential of metal-organic frameworks Empowering academics Athena SWAN success Bio-power Developing an implantable biofuel cell Education at the cutting edge Innovative teaching and learning techniques

2016

In this issue Welcome to Chemistry New Boundaries. In December 2014, we received the results of the 2014 Research Excellence Framework (REF); we were delighted to be ranked eighth for research power and sixth for research intensity among all UK chemistry departments. All staff contributed to our REF success and it was great to see the innovative chemistry we develop here at Southampton, and its real-world impact, recognised by the REF panel. In 2015 we were also very pleased to receive an Athena SWAN Silver Award, recognising our dedication to equality and diversity.

This issue of Chemistry New Boundaries reflects these recent successes. You will find out about some of our world-leading research projects and our work at the cutting edge of chemical education. You will also hear about our excellent team of glassblowers, the experiences of one of our undergraduates on a placement at NASA and our work on improving the sustainability of our activities. Our strong international links with A*STAR in Singapore are also highlighted. Iâ&#x20AC;&#x2122;m currently in my sixth and final year as Head of Chemistry. Looking back over my time as Head, I feel immensely proud of the achievements of all our staff and students. It has been a great pleasure and privilege to lead the department through this period and I thank everyone in Chemistry for their support. Professor Phil Gale Head of Chemistry November 2015 For more information, visit our website www.southampton.ac.uk/chemistry/research

Please send us your feedback We are keen to receive any feedback you have about Chemistry New Boundaries. If you have any comments or suggestions, please send them to chemistryresearch@southampton.ac.uk

1 Materials innovation Unlocking the potential of metal-organic frameworks. Page 4

2 Empowering academics

Athena SWAN success. Page 10

3 Bio-power

Developing an implantable biofuel cell. Page 12

4 Education at the cutting edge Innovative teaching and learning techniques. Page 16

More highlights Glassblowing expertise The University is home to one of the few scientific glassblowing facilities in the UK. Page 19 Research with NASA Undergraduate chemistry student Jamie Thompson is currently a research associate at NASAâ&#x20AC;&#x2122;s Ames Research Centre. Page 20 Global partnerships Research collaboration with the Agency for Science, Technology and Research (A*STAR) in Singapore. Page 21

Materials innovation A Southampton research team is enhancing the properties of an intriguing group of compounds with potential applications ranging from sustainable energy to drug delivery. New Boundaries finds out more.

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â&#x20AC;&#x153;Our aim is to develop experimental protocols and establish proof of principle. Using that underpinning knowledge, MOFs can be configured with the characteristics required for specific uses.â&#x20AC;? Dr Darren Bradshaw, Head of Functional Inorganic, Materials and Supramolecular Chemistry

MOF capsules with a fluorescent enzyme concentrated in the shell

Chemistry New Boundaries | University of Southampton

Metal-organic frameworks (MOFs) are compounds that consist of metal ions linked by rigid organic (carbon-containing) molecules to form an open network. “There are around 50,000 known MOFs,” says Dr Darren Bradshaw, Head of Functional Inorganic, Materials and Supramolecular Chemistry at the University. “The enormous number of possible combinations of metal ions and organic linkers means they are chemically very versatile with all sorts of potential applications.”

European Research Council, they have been developing new ways to process MOFs into application-specific configurations – one of the few MOF research groups in the UK with this focus.

Practical properties

One of the team’s innovations is the use of MOFs to make microcapsules. Microcapsules have a wide range of uses – from biomedical and pharmaceutical functions to flavourings and fragrances, including ‘scratch and sniff’ technology.

“MOFs are highly porous, containing lots of holes like a bath sponge,” continues Darren, “but in MOFs the holes are as small as molecules. This results in low density and a huge surface area; the most porous MOFs have an internal surface area equivalent to a football field, around 8,000 to 10,000 metres squared per gram of material.”

Darren says: “Our aim is to develop experimental protocols and establish proof of principle. Using that underpinning knowledge, MOFs can be configured with the characteristics required for specific uses.” ‘MOFsomes’

“In simple terms, if you have an emulsion droplet, such as an oil droplet in water, particles will assemble at the interface,” says Darren. “You can lock these particles MOFs can also be assembled into complex together to make a colloidosome – a hollow structures and, because they are hybrids, have spherical structure. However, the large gaps the functionality of the metal components between the particles mean the structure and of the organic parts. Depending on the can’t be used to store molecules. We chosen building blocks, the MOF can be discovered that we could do the same with tuned to exploit these functions. microporous MOF particles, and, by filling in the gaps between, enable the capsule to carry Because of the possibilities offered by this a molecular cargo.” combination of characteristics, MOFs have attracted significant research attention in The capsules, named ‘MOFsomes’ by the recent years, particularly for environmental team, take the form of a hollow polymer applications. The porosity of MOFs means network with MOF particles locked into the they can be used to filter carbon dioxide outer surface. Acid can be used to dissolve from flue gases, for example, and their huge the MOF micropores to enable molecules surface area offers a way to store biofuels to escape through the polymer network, such as methane. They can also be used for creating an acid-triggered release system. the separation of molecules and for catalysis These findings, published in Advanced (the speeding up of chemical reactions) to enhance a range of pharmaceutical, chemical Materials in 2013, suggest that MOFsomes could have a part to play in targeted drug and manufacturing processes. treatments in the future. Many drug delivery While some MOFs are already being offered systems are based on acid release, particularly commercially, this is a vast field of research in cancer treatments because of the slightly and there are countless ways in which MOFs acidic environment around cancer cells. } could be used to solve real-world challenges. This is where Darren and his research team come in. Funded by a five-year grant from the

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“Our work to date has identified some clear opportunities for commercialisation and we’re interested in finding ways to scale up MOF production and extend the use of MOFs to address new challenges.” Dr Darren Bradshaw, Head of Functional Inorganic, Materials and Supramolecular Chemistry

Encapsulating enzymes As well as creating new types of microcapsule, the research team has discovered an effective way of putting biomolecules such as enzymes into MOF capsules to enhance their catalytic abilities. The researchers used Candida antarctica lipase B, a robust enzyme that has been the subject of many prior studies, enabling easy benchmarking of the results.

the size of the MOF pores. In addition, the researchers also co-incorporated magnetite into the capsules so that they can be easily recovered by a magnet reused – the study demonstrated that the enzymes remained active over six cycles of use.

This research, published in Chemical Science in 2015, demonstrates the potential for MOFs in size-selective, recyclable catalysis “It’s possible to add the enzyme directly when for applications such as chemical sensing or synthesising the MOF,” explains Darren, “but the development of biomarkers for use in diagnostic tests. this leads to the enzyme being immobilised in a crystal ‘prison’ without enough space to Taking inspiration from nature work effectively. Our method of configuring Alongside the work on capsules, the team the MOF capsule around the enzyme allows investigated whether the principles of the enzyme to move freely. It’s too large to biomineralisation could be applied to leave the capsule through the MOF pores but MOFs. Biomineralisation is the body’s smaller molecules can move in and out.” mechanism for depositing inorganic minerals for specialist functions, such as calcium The encapsulated enzyme was five times phosphate for bone formation. The process is more active than the free enzyme under highly controlled in nature, using assemblies the conditions tested, making this method of organic molecules to deposit particles of catalysis highly efficient, and molecular of a strictly defined size and shape, often in access to the enzyme can be controlled by

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intricate structures that are very difficult to replicate in the laboratory. The researchers experimented with MOFs grown in gelatin pellets and found that this created a favourable environment for framework growth. “We found that the gelatin controls not only crystal growth chemistry but also the shape of the crystals,” says Darren. “This is exactly what happens in matrix-mediated biomineralisation processes. Gelatin is also soluble under certain conditions, and by varying the amount of added gelatin to MOF syntheses we can also control their particle size – for example, to scale down particles for use in drug delivery.” Improving molecule separation Another challenge the team has tackled is the separation of molecules in liquids that have traditionally been very difficult to isolate from one another. The research focused on the aromatic hydrocarbon xylene, which is composed of three molecular components

called isomers. Separating the isomers using the usual method of distillation is problematic because their boiling points are very similar, so the study looked at separation using a chromatographic column.

these outcomes further. “Our work to date has identified some clear opportunities for commercialisation and we’re interested in finding ways to scale up MOF production and extend the use of MOFs to address new challenges.”

To counteract some of the drawbacks of To find out more, visit using pure MOFs in this process, the team www.southampton.ac.uk/darrenexperimented with a MOF/silica composite. The study, which was published in the Journal bradshaw of Materials Chemistry in 2013 with colleagues from the University of Liverpool, showed that the combination of materials enabled the effective and rapid separation of the three isomers. These findings could have implications for industry, as one of the three isomers, the para-isomer, is highly valued for its use in the manufacture of polyesters; around 80 per cent of xylene production is geared up to making this isomer. With the ERC-funded work now coming to an end, Darren is keen to explore some of

Chemistry New Boundaries | University of Southampton

Empowering academics This year Chemistry at Southampton was proud to receive an Athena SWAN Silver Award, recognising our continuing commitment to gender equality. Andrea Russell, Professor of Physical Electrochemistry, talks about her research and explains how she has helped to shape – and benefited from – the department’s supportive culture.

What is your area of research?

As an electrochemist and spectroscopist, my research involves developing methods that look at the electrochemical interface, in particular electrocatalysis (modification of the rate of an electrochemical reaction). One problem my research group is working on relates to the electrochemical processes of oxygen reduction and oxygen evolution. These reactions are important in technologies such as water electrolysers that enable the production of hydrogen for renewable energy, batteries to store energy and fuel cells for environment-friendly, hydrogen-powered cars. The most widely used platinum-based catalysts are expensive and not effective in some environments, so cheaper, better catalysts are needed. Using a variety of spectroscopic and structural techniques combined with electrochemical measurements, our aim is to characterise the activity of alternative catalysts to understand what aspects make them more effective.

What makes Southampton a good place for this work?

If you look around the world, this is probably one of the top four electrochemistry groups. It covers the breadth of electrochemistry and I’ve got fantastic, expert colleagues to work with. The department’s world-class reputation is the reason I wanted a job here and I’m very proud to be contributing to its work.

What links do you have beyond the University?

Much of my group’s research involves industry collaboration and we work with companies including Johnson Matthey, ITM Power, C-Tech Innovation and City Technology. Our research makes extensive use of national synchrotron radiation facilities such as the UK’s Diamond Light Source and the Stanford Synchrotron Radiation Lightsource in the United States. I’m also involved in a number of expert groups – for example I’m Chair of the Physical Electrochemistry Division of the International Society of Electrochemistry and an active member of the UK Catalysis Hub.

What is your involvement in the Athena SWAN programme at Southampton?

Athena SWAN (Scientific Women’s Academic Network) encourages and recognises efforts to support the career aspirations of women and removes gender bias in higher education and research. I’m involved in Athena SWAN at Southampton through the University’s Women in Science, Engineering and Technology (WiSET) group. I led Chemistry’s successful Bronze Award submission in 2013 and I’m delighted that this year’s submission for a Silver Award, led by Dr Lynda Brown, was also successful. As a department it’s great to be recognised for all the efforts we’ve made.

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The process helped us to identify areas of strength and to develop areas of Chemistry’s culture and procedures, such as the introduction of more flexible working arrangements and ensuring female representation on committees and among invited speakers, to project the message that women are part of a successful chemistry department. Of course, Athena SWAN doesn’t just benefit women; by helping to remove the barriers to career progression for women, it removes them for everyone.

ow have you benefited from this H supportive culture?

From the day I arrived in 1997 I have always felt welcome here at Southampton; I can contribute and I know those contributions are appreciated. At every stage of my career I was encouraged to apply for promotion, with support from colleagues in Chemistry and through initiatives such as peer support networks for female academics and the Senior Management Development Programme, which enabled me to develop my leadership skills and to extend my network of contacts beyond Chemistry. Now, as a professor, I’m pleased to be able to offer that support to my junior colleagues. I serve as a mentor for colleagues in Chemistry, for example, and I’m a speaker on the Springboard programme, which helps women identify their strengths and take steps to improve their career opportunities.

ow do you balance your research H and teaching roles?

For me, teaching is equally important as my research. Indeed, the two are closely connected – so far 27 PhD students have completed their research degrees at Southampton under my supervision. As Director of Programmes I care passionately about delivering high-quality degree courses for our students. One challenge we’re facing is increasing student numbers, which is an excellent challenge to have – it’s wonderful that so many people want to come and study here. It does mean that we need to manage the workloads of staff so that they are able to excel in their research as well as their teaching.

hat aspect of your work do you find W most satisfying?

One of the greatest rewards for me is watching students walk across the stage to receive their awards at graduation. The biggest product of Chemistry at Southampton is its people – and we produce some great people. For more information, please visit www.southampton.ac.uk/andrea-russell

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Bio-power Southampton chemists are part of an international team working to develop an implantable biofuel cell. New Boundaries finds out more.

Chemistry New Boundaries | University of Southampton

The research team is designing new ways to ‘wire up’ enzymes in the body that metabolise glucose, to generate an electric current, generating power in a small biofuel cell. The idea is to create a biofuel cell that can be implanted into an artery and use glucose in the bloodstream as an energy source; this could then be used to power sensors or other devices implanted in a patient, for example to monitor blood-sugar levels, improve muscle control or power implants. Creating an implantable biofuel cell is a challenging, long-term goal. Enzymes are large, folded proteins; their active sites – where the reaction happens – are wrapped up inside the structure and difficult to access, an obstacle the researchers needed to overcome. “What we are doing is very exciting,” says Professor Phil Bartlett, Head of Electrochemistry, at the University. “We are working with researchers from across Europe who are engineering the enzymes that can be attached to the electrode surfaces we are developing, and then put into fuel cells.” Engineering enzymes Using a novel modular assembly method they have designed, the Southampton researchers are building up electrodes of the desired size and shape with building blocks of carbon nanotubes, just a few nanometres in diameter. “Using electrochemistry we can make a bond between the electrode and a coupling molecule on the enzyme surface, building the electrode up piece by piece,” says Phil. Co-workers at the University of Natural Resources and Life Science, Vienna, are genetically modifying the enzyme so that the active site is more accessible by adding a thiol (sulphur and hydrogen-containing) group on the enzyme surface, which the molecules on the electrode clip onto like a plug in a socket. “Thanks to X-ray crystallography, we have the 3D crystal structure of cellobiose

dehydrogenase, the enzyme we are testing, and we therefore know where all the amino acids are located; this means we can precisely modify the enzyme to suit our requirements,” says Phil. The molecule on the surface of the electrode, a maleimide (hydrogen, nitrogen and oxygencontaining) group, reacts spontaneously with the thiol to create a covalent bond and attaches to the surface of the enzyme. “We can put these thiol groups at different places on the enzyme to work out the most effective configuration of enzyme on the electrode,” says Phil. For the biofuel cell, the team repeat this process with a second electrode that reacts with oxygen. “We can measure the electric current flowing across the electrode, which is a direct measure of how fast the enzyme is reacting; it’s like a little molecular machine,” says Phil. Fundamental studies Using a model electrode, comprising of a mat of carbon nanotubes, and varying the conditions such as acidity and the presence of calcium, the team is building up an understanding of the kinetics of the system. These fundamental studies are important because the researchers need to understand the fine detail of how the system works before they can use this enzyme on electrode surfaces with a much higher surface area to give more power. “What interests me is how to build these molecular machines; we want to understand how we can make the enzyme go faster, and to do that, we need to isolate the rate-limiting step of the reaction,” says Phil. Funded by the Marie Curie International Training Network, the project is part of an EU scheme that is designed to train PhD students in bioelectrochemistry. It involves universities from across Europe and also several companies. “There are students from

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all over the EU collaborating on this project,” says Phil. “Although it seems like a very challenging long-term project, the steps along the way have immediate benefit, for example for improving non-implantable diagnostic devices such as blood cholesterol tests. It also provides a grand challenge to draw all the students together.” International recognition “I have been interested in bioelectrochemistry since completing my PhD. It’s fascinating how electron transfer in biological processes works and it also provides excellent challenges for us to create new systems based on these natural processes,” says Phil, who was recently awarded the Giulio Milazzo Prize for his contribution to bioelectrochemistry throughout his career. “The field of bioelectrochemistry has changed a great deal since I started my research in this area in the 1980s; now with genetic engineering and X-ray crystallography, it has become much more sophisticated and powerful because we can now mutate and design enzymes to work with electrodes,” says Phil. “In the future, as new methods of selecting enzymes, such as ‘directed evolution’, emerge, this is only going to continue.” For more information, visit www.southampton.ac.uk/phil-bartlett

â&#x20AC;&#x153;What interests me is how to build these molecular machines; we want to understand how we can make the enzyme go faster, and to do that, we need to isolate the rate-limiting step of the reaction,â&#x20AC;? Professor Phil Bartlett, Head of Electrochemistry

Enzyme structure showing the modification site in pink

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Education at the cutting edge By introducing and evaluating innovative teaching and learning techniques, David Read, Professorial Fellow in Chemical Education, is helping to drive up the quality of education for chemistry students at Southampton and beyond.

How did you become interested in education research?

I initially trained as a secondary school teacher and during that period there were lots of initiatives from the government regarding how to teach effectively. The question in my mind was always ‘what is the evidence for doing things this way?’ When I joined the University as a School Teacher Fellow in 2007 I knew it would be important to measure the impact of new teaching methods so that I could demonstrate their effectiveness to my colleagues. This evidence gathering has led to around 20 published articles, and is now developing into genuine chemical education research.

Are you engaged in collaborative research?

I’m involved in a project with a colleague here and others at the universities of Birmingham, Keele, Leeds and East Anglia. The aim is to create a ‘chemical concept inventory’ – a questionnaire designed to identify whether students have grasped a particular concept – that will provide a robust way of measuring the impact of teaching. By working collaboratively we can draw from a broader pool of expertise and test the inventories on a larger sample of students.

Does your work have an impact beyond the University?

For me, education research is only worth doing if it will make a difference in the wider world, so I’m really pleased that we’ve been able to see our ideas being put into practice. One of the first things I introduced was the For example, last year I supervised a student use of an electronic voting system to engage who developed a video mark scheme for A students during lectures. I helped staff to level chemistry students, which we trialled incorporate this into their teaching and in 18 schools and colleges with 550 students. evaluated it using student questionnaires. The feedback was overwhelmingly positive Another project looked at students’ use of online video lectures – this was before putting and teachers have since approached me about making their own mark schemes. lectures online became common practice. I also introduced an online video mark scheme What is your role in the Undergraduate in which an expert talks through the thought Ambassador Scheme? process underpinning the answers to an The Undergraduate Ambassador Scheme is assignment. This enables students to mark a nationwide programme that was set up in their own work and helps them to develop their capacity for self-criticism. A survey that 2002 because of concerns about the shortage of maths and science teachers. I established it captured students’ reflections on the selfwithin Chemistry in 2009 and am the module assessment process showed that many were coordinator. Under the scheme, students modifying their thinking as a result. undertake a classroom-based project in a It’s a team effort – undergraduate project school, which usually involves doing some students have been involved in gathering teaching and evaluating its impact. The aim and evaluating evidence and we now have is to help students decide whether to follow three postgraduates working on education a career in teaching, as well as to promote research projects. higher education within schools.

What types of learning technology have you introduced and evaluated?

What are the challenges of your area of work?

Going from scientific research to education research is a big step; it requires a completely different mindset. In education research you’re working with human subjects, so there’s a much greater degree of uncertainty and the evidence is more subjective. It can be difficult for scientists to take that step and it’s something I’m still working towards.

What are your proudest achievements?

My work has been recognised with awards from the University, the Royal Society of Chemistry and the Association for Learning Technology. But the award I’m most proud of is the Faculty of Natural and Environmental Sciences Lifetime Achievement Award: Teaching and Learning, which I received in 2014. I was nominated by students and reading their comments made me realise that what I do is really appreciated. So that’s the award that put the biggest smile on my face! I’m also proud that my colleagues are now coming to me to ask how to put new teaching techniques into practice. They are seeing the value of educational innovations and I’m able to play a part in their career development. For more information, visit www.southampton.ac.uk/david-read

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In brief

Leading scientific mind

Towards new cancer therapies Prestigious award for A Southampton-led research team has received Chemistry researcher

Professor Phil Gale, Head of Chemistry, has been listed as one of the world’s most influential funding from Cancer Research UK (CRUK) to scientific minds in the Thomson Reuters Highly identify and develop new compounds to tackle Cited Researchers 2015 rankings. one of the most difficult to treat cancers. Phil’s research interests focus on the supramolecular chemistry of anionic species (atoms that have gained electrons, giving them a negative charge), in particular the molecular recognition, sensing and transport of anions across membranes in the body. Transmembrane anion transporters have potential applications in the development of future treatments for cystic fibrosis and cancer. Phil is the author or co-author of over 200 publications. He serves as the Chair of Chemical Society Reviews editorial board and is a member of the advisory board of Chemical Science. He is also the co-editor of Supramolecular Chemistry, and a member of the international editorial advisory boards of Coordination Chemistry Reviews and the Encyclopaedia of Supramolecular Chemistry. Phil has won a number of research prizes, most recently the Royal Society of Chemistry (RSC) 2014 Supramolecular Chemistry Award, and a Royal Society Wolfson Research Merit Award (2013). “I was delighted to be one of seven chemists in the UK recognised for the academic impact of their work by Thomson Reuters in 2015,” says Phil. “The challenge for us is to take our fundamental understanding of anion transporter design and apply it in biological systems to produce new treatments for disease. We have begun to address this significant challenge.”

Tumours caused by mutations in the KRAS gene are often unresponsive to traditional therapies. The researchers are developing new compounds to block the interaction between the KRAS protein product and another protein, phosphoinisitide-3-kinase (PI3K) p110α, which is a critical step in the formation of lung and pancreatic cancers. The compounds developed during this programme will form a significant step towards a treatment for this type of cancer. Ali Tavassoli, Professor in Chemical Biology, and his team at the University will be working in collaboration with Professor Julian Downward of the Francis Crick Research Institute and Dr Esther Castellano-Sanchez at Bart’s Cancer Institute. “I am very grateful to be the recipient of a programme foundation award from CRUK and excited to be working with an internationally leading cancer cell biologist to develop new cancer therapeutics,” says Ali. “The duration of this award and level of support given to us by CRUK demonstrates the importance of KRAS as a cancer target and my lab’s reputation for being world leaders in developing first-in-class inhibitors against the most challenging targets.”

Chemistry New Boundaries | University of Southampton

Malcolm Levitt, Professor of Physical Chemistry and Head of Magnetic Resonance, has been awarded the Russell Varian Prize 2015. Malcolm was presented with the prize on 5 July 2015, at the EUROMAR 2015 Congress in Prague, for his article entitled Nuclear Magnetic Resonance (NMR) population inversion using a composite pulse, which was published in 1979 in the Journal of Magnetic Resonance. Malcolm invented the composite pulses that are now routinely used in the great majority of multidimensional and heteronuclear NMR experiments. NMR is a method used by physicists, chemists, and biologists to investigate the molecular structure of matter. In the form of magnetic resonance imaging (MRI), the method is widely used in hospitals to make three-dimensional images of the interior of the human body. “It is very gratifying that a neat trick I devised as an undergraduate project student in Oxford has been selected for such a prominent award in the field of nuclear magnetic resonance,” he says. The Russell Varian prize honours the memory of the pioneer behind the first commercial Nuclear Magnetic Resonance (NMR) spectrometers. It is awarded to a researcher who has made a significant innovative contribution to state-of-the-art NMR technology.

Glassblowing expertise The University is home to one of the few scientific glassblowing facilities in the UK. With a comprehensive range of equipment to manufacture complex scientific glassware, the University’s glassblowing workshop provides a valuable service for researchers in academia and industry. The experienced staff team has many years’ experience in the design and construction of specialised glassware used for research and development. Members of the team attend symposia around the world and glassblower

Lee Mulholland sits on the British Society of Scientific Glassblowers’ board of examiners and gives talks and demonstrations of scientific glassblowing. As well as providing equipment to support teaching and research within the University, the team also caters for external industrial contracts. Recent clients have included the universities of Iceland and Oxford, Imperial College London, Merck, QinetiQ, and Ventacon UK.

“The University of Southampton’s glassblowers have supplied Ventacon for over 20 years with outstanding quality, highly specialised glassware for our spectroscopy products. Nothing has been impossible to achieve for us and these experts in their field of scientific glassblowing have also been pleased to help in the R&D of some of our more demanding products,” comments one client, Paul Hendra, director of Ventacon UK.

Chemistry New Boundaries | University of Southampton

In brief Research with NASA Undergraduate chemistry student Jamie Thompson is currently a research associate at NASA’s Ames Research Centre for his MChem placement year.

missions and also siphon off useful hydrocarbon products.

“So far my time here at NASA’s Ames Research Centre has been extremely inspiring,” says Jamie. “Knowing that one day Jamie is part of a team designing a my work could help astronauts explore more photoelectrocatalyst based on artificial of the universe drives me to get straight into leaves, utilising solar radiation to convert carbon dioxide and water into hydrocarbons. the lab every day. Southampton’s support has Led by NASA materials scientist Dr Bin Chen, allowed me to take the first small step the researchers aim to create a device that can towards becoming an astronaut myself.” recycle oxygen on long-duration space

Image courtesy of Witold Koning

Chemistry New Boundaries | University of Southampton

Jamie recently contributed to the successful proposal for the work to receive phase II funding from the prestigious NASA Innovative Advanced Concepts (NIAC) programme. At Southampton, Jamie’s degree is focused on electrochemistry and material science. His placement is funded by the University and the Royal Society of Chemistry. He will be presenting on the project at the MRS Fall meeting in Boston later this year.

Taking technology smaller

Global partnerships

Sustainability success

Southampton researchers demonstrated their pioneering research using electrochemistry to deposit materials for creating nano-devices just a few atoms in diameter, at the Royal Society’s annual Summer Science Exhibition in July 2015.

Southampton chemists have been establishing new international collaborations at worldleading research centres across the globe, giving the next generation of chemists the chance to experience global study.

A team of students and staff in Chemistry have been recognised at this year’s Sustainability Action Awards.

Chemistry researchers demonstrated a revolutionary technique that uses supercritical fluid electrodeposition (SCFED) to build ultra-small circuitry, which offers the exciting prospect of ‘growing’ advanced nanomaterials and devices atom-by-atom. Visitors were able to electroplate their fingerprints in gold, operate an experiment showing how supercritical fluids work and speak to scientists about their research at the exhibition which attracted over 13, 000 visitors.

Since 2009, Southampton has been a partner with the Agency for Science, Technology and Research (A*STAR), a statutory board under the Ministry of Trade and Industry of Singapore. Recently, researchers led by Head of Chemistry Professor Phil Gale and Dr Robert Raja, held discussions with scientists at A*STAR to discuss mutual interests and potential future collaborative projects.

Colleagues from Physics also showed visitors their innovative water transistor model of how circuits work, using water to represent electrons, water flow to represent current, and water pressure to control flow through a channel representing voltage. “The level of enthusiasm from the public was particularly inspiring; it enabled us to engage directly with them on a topic that is technically challenging and cutting-edge, showing the potential relevance of the research to society, as well as the importance of multidisciplinary research teams,” says Professor Gill Reid, one of the project leaders.

“Many of our colleagues who visited Singapore and China had joined Southampton Chemistry over the last few years and we wanted to help them build new research links with our strategically important partner institutions,” says Phil. “The visits combined symposia with one-to-one meetings between the researchers – you could describe the process as scientific ‘speed dating’,” he adds.

Through A*STAR’s Research Attachment Programme (ARAP), PhD students studying chemistry, medicine or engineering can spend two years at an A*STAR research institute. “Our chemists studying a range of topics from biochemistry, sustainable catalysis and antitumour agents, to DNA biomarkers and metalorganic frameworks have been able to take The SCFED Project is funded by the Engineering advantage of new techniques, insights and ideas and Physical Sciences Research Council from international colleagues,” explains Robert. (EPSRC) through a flagship programme grant.

The team took home the Outstanding Student and Staff Team award for their ‘Try before you buy’ initiative. ‘Try before you buy’ is a sustainable synthetic chemistry research laboratory, in which staff can trial new equipment, incorporate sustainability into the curriculum and empower colleagues to try new approaches to their area of research. “It is a wonderful honour to receive this award and a fitting testament to the efforts of numerous people in the department, and across the University, who strongly believe we can and should operate in a more environmentally sustainable way,” says team member Dr Simon Coles, Associate Professor and Director of the National Crystallography Service. Following the award, the Excel placement scheme funded five ‘sustainability’ summer interns, who used ‘design of experiment’ approaches to optimise common reactions carried out in research teams across Chemistry. “Much like the ‘Try before you buy’ initiative, the bigger picture is a behaviour and best practice change. Over time, these small changes will translate into large reductions in utilities and waste, and help us increase our sustainable working practices,” says Simon. For more information on these stories, visit www.southampton.ac.uk/chemistry/ research

Chemistry New Boundaries | University of Southampton

Journal papers published in 2014–2015 Fischlechner, M; Schaerli, Y; Mohamed, M F; Patil, S; Abell, C; Hollfelder, F Evolution of enzyme catalysts caged in biomimetic gel-shell beads Nature Chemistry, 2014, 6, 791–796 Kim, Y Y; Schenk, A S; Ihli, J; Kulak, A N; Hetherington, N B J ; Tang, C C; Schmahl, W W; Griesshaber, E; Hyett, G; Meldrum, F C A critical analysis of calcium carbonate mesocrystals Nature Communications, 2014, 5, DOI: 10.1038/ncomms5341 Qamhieh, K; Nylander, T; Black, C F; Attard, G S; Dias, R S; Ainalem, M L Complexes formed between DNA and poly(amido amine) dendrimers of different generations – modelling DNA wrapping and penetration Physical Chemistry Chemical Physics, 2014, 16, 13,112–13,122 Bartlett, P N; Benjamin, S L; de Groot, C H; Hector, A L; Huang, R M; Jolleys, A; Kissling, G P; Levason, W; Pearce, S J; Reid, G; Wang, Y D Non-aqueous electrodeposition of functional semiconducting metal chalcogenides: Ge2Sb2Te5 phase change memory Materials Horizons, 2015, 2, 420–426 Becker-Baldus, J; Bamann, C; Saxena, K; Gustmann, H; Brown, L J; Brown, R C D; Reiter, C ; Bamberg, E; Wachtveitl, J; Schwalbe, H; Glaubitz, C Enlightening the photoactive site of channelrhodopsin-2 by DNPenhanced solid-state NMR spectroscopy Proceedings of the National Academy of Sciences of the United States of America, 2015, 112, 9896–9901 Nyman, J; Day, G M Static and lattice vibrational energy differences between polymorphs Crystengcomm, 2015, 17, 5154–5165 Dinis, P; Suess, D L M; Fox, S J; Harmer, J E; Driesener, R C; De La Paz, L; Swartz, J R; Essex, J W; Britt, R D; Roach, P L X-ray crystallographic and EPR spectroscopic analysis of HydG, a maturase in [FeFe]-hydrogenase H-cluster assembly Proceedings of the National Academy of Sciences of the United States of America, 2015, 112, 1362–1367 Badiola, K A; Bird, C; Brocklesby, W S; Casson, J; Chapman, R T; Coles, S J; Cronshaw, J R; Fisher, A; Frey, J G; Gloria, D Experiences with a researcher-centric ELN Chemical Science, 2015, 6, 1614–1629 Wu, X; Busschaert, N; Wells, N J; Jiang, Y B; Gale, P A Dynamic covalent transport of amino acids across lipid bilayers Journal of the American Chemical Society, 2015, 137, 1476–1484 Ralph, M J; Harrowven, D C; Gaulier, S; Ng, S; Booker-Milburn, K I The profound effect of the ring size in the electrocyclic opening of cyclobutene-fused bicyclic systems Angewandte Chemie-International Edition, 2015, 54, 1527–1531 Yada, C; Lee, C E; Laughman, D; Hannah, L; Iba, H; Hayden, B E A high-throughput approach developing lithium-niobium-tantalum oxides as electrolyte/cathode interlayers for high-voltage all-solid-state lithium batteries Journal of the Electrochemical Society, 2015, A722–A726

Chemistry New Boundaries | University of Southampton

Robertson, C; Beanland, R; Boden, S A; Hector, A L; Kashtiban, R J; Sloan, J; Smith, D C; Walcarius, A Ordered mesoporous silica films with pores oriented perpendicular to a titanium nitride substrate Physical Chemistry Chemical Physics, 2015, 17, 4763–4770 Meier, B; Mamone, S; Concistre, M; Alonso-Valdesueiro, J; Krachmalnicoff, A; Whitby, R J; Levitt, M H Electrical detection of ortho-para conversion in fullereneencapsulated water Nature Communications, 2015, 6, DOI: 10.1038/ncomms9112 van Straaten, K E; Kuttiyatveeti, J R A; Sevrain, C M; Villaume, S A; Jimenez-Barbero, J; Linclau, B; Vincent, S P; Sanders, D A R Structural basis of ligand binding to udp-galactopyranose mutase from mycobacterium tuberculosis using substrate and tetrafluorinated substrate analogues Journal of the American Chemical Society, 2015, 137, 1230–1244 Li, XJ; Hector, A L; Owen, J R Evaluation of Cu3N and CuO as negative electrode materials for sodium batteries Journal of Physical Chemistry C, 2014, 118, 29,568–29,573 Carravetta, M; Concistre, M; Levason, W; Reid, G; Zhang, W J Unique Group 1 cations stabilised by homoleptic neutral phosphine coordination Chemical Communications, 2015, 51, 9,555–9,558 Harmer, J E; Hiscox, M J; Dinis, P C; Fox, S J; Iliopoulos, A; Hussey, J E; Sandy, J; Van Beek, F T; Essex, J W; Roach, P L Structures of lipoyl synthase reveal a compact active site for controlling sequential sulfur insertion reactions Biochemical Journal, 2014, 464, 123–133 Puthiyapura, V K; Brett, D J L; Russell, A E; Lin, W F; Hardacre, C Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel Chemical Communications, 2015, 51 Issue, 13,412–13,415 Sampson, C; Fox, T ; Tautermann, C S; Woods, C; Skylaris, C K A “stepping stone” approach for obtaining quantum free energies of hydration Journal of Physical Chemistry B, 2015, 119, 7,030–7,040 Mistry, I N; Smith, P J S; Wilson, D I; Tavassoli, A Probing the epigenetic regulation of HIF-1 alpha transcription in developing tissue Molecular Biosystems, 2015, 11, 2,780–2,785 Utz, M; Levitt, M H; Cooper, N; Ulbricht, H Visualisation of quantum evolution in the Stern-Gerlach and Rabi experiments Physical Chemistry Chemical Physics, 2015, 17, 3,867–3,872 Kilpin, K J; Goodman, J M; Johnson, A P; Whitby, R J Dial-a-molecule workshop: computational prediction of reaction outcomes and optimum synthetic routes Chemistry Central Journal, 2015, 9, DOI: 10.1186/s13065-015-0129-9

This selection of journal papers demonstrates the breadth of chemistry research undertaken by Southampton academics. For more research papers, please view individual staff profiles online. Hylton, R K; Tizzard, G J; Threlfall, T L; Ellis, A L; Coles, S J; Seaton, C C; Schulze, E; Lorenz, H; Seidel-Morgenstern, A; Stein, M; Price, S L Are the crystal structures of enantiopure and racemic mandelic acids determined by kinetics or thermodynamics? Journal of the American Chemical Society, 2015, 137, 11,095–11,104 Perry, S C; Al Shandoudi, L M; Denuault, G Sampled-current voltammetry at microdisk electrodes: kinetic information from pseudo steady state voltammograms Analytical Chemistry, 2014, 86, 9,917–9,923 Berglund, N A; Piggot, T J; Jefferies, D; Sessions, R B; Bond, P J; Khalid, S Interaction of the antimicrobial peptide polymyxin b1 with both membranes of E. coli: a molecular dynamics study PLOS Computational Biology, 2015, 11, DOI: 10.1371/journal.pcbi.1004180 Kuprov, I; Hodgson, D M; Kloesges, J; Pearson, C I; Odell, B; Claridge, T D W Anomalous nuclear overhauser effects in carbon-substituted aziridines: scalar cross-relaxation of the first kind Angewandte Chemie-International Edition, 2015, 54, 3,697–3,701 Ratsameepakai, W; Hemiman, J M; Jenkins, T J; Langley, G J Evaluation of ultrahigh-performance supercritical fluid chromatographymass spectrometry as an alternative approach for the analysis of fatty acid methyl esters in aviation turbine fuel Energy & Fuels, 2015, 29, 2,485–2,492 Prasad, A; Huefner, A; Mahajan, S; Seshia, A A Investigating biomechanical noise in neuroblastoma cells using the quartz crystal microbalance Journal of the Royal Society Interface, 2015, 12, DOI: 10.1098/rsif.2014.1389 Potter, M E; Paterson, A J; Mishra, B; Kelly, S D; Bare, S R; Cora, F; Levy, A B; Raja, R Spectroscopic and computational insights on catalytic synergy in bimetallic aluminophosphate catalysts Journal of the American Chemical Society, 2015, 137, 8534–8540 Ceban, V; Olomola, T O; Meazza, M; Rios, R Highly diastereoselective synthesis of spiropyrazolones Molecules, 2015, 20, 8,574–8,582

Rodriguez, P; Garcia-Araez, N; Herrero, E; Feliu, J M New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes Electrochimica Acta, 2015, 151, 319–325 Harimech, P K; Gerrard, S R; El-Sagheer, A H; Brown, T; Kanaras, A G Reversible ligation of programmed DNA-gold nanoparticle assemblies Journal of the American Chemical Society, 2015, 137, 9,242–9,245 Kotova, O; Blasco, S; Twamley, B; O’Brien, J; Peacock, R D; Kitchen, J A; Martinez-Calvo, M; Gunnlaugsson, T The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures Chemical Science, 2015, 6, 457–471 Illy, B N; Ingham, B; Toney, M F; Nandhakumar, I; Ryan, M P Understanding the selective etching of electrodeposited ZnO nanorods Langmuir, 2014, 30, 14079–14085 Stevanato, G; Hill-Cousins, J T; Hakansson, P; Roy, S S; Brown, L J; Brown, R C D; Pileio, G; Levitt, M H A nuclear singlet lifetime of more than one hour in room-temperature solution Angewandte Chemie-International Edition, 2015, 54, 3,740–3,743 Krachmalnicoff, A; Bounds, R; Mamone, S; Levitt, M H; Carravetta, M; Whitby, R J Synthesis and characterisation of an open-cage fullerene encapsulating hydrogen fluoride Chemical Communications, 2015, 51, 4993–4996 Neal, E A; Goldup, S M Competitive formation of homocircuit [3]rotaxanes in synthetically useful yields in the bipyridine-mediated active template CuAAC reaction Chemical Science, 2015, 6, 2,398-2,404 Galinis, G; Luna, L G M; Watkins, M J; Ellis, A M; Minns, R S; Mladenovic, M; Lewerenz, M; Chapman, R T; Turcu, I C E; Cacho, C Formation of coherent rotational wavepackets in small molecule-helium clusters using impulsive alignment Faraday Discussions, 2014, 171, 195–218

Kongsuphol, P; Ng, H H; Pursey, J P; Arya, S K; Wong, C C; Stulz, E; Park, M K EIS-based biosensor for ultra-sensitive detection of TNF-alpha from nondiluted human serum Biosensors & bioelectronics, 2014, 61, 274–279 Huo, J; Aguilera-Sigalat, J; El-Hankari, S; Bradshaw, D Magnetic MOF microreactors for recyclable size-selective biocatalysis Chemical Science, 2015, 6, 1,938–1,943 Howlin, R P; Fabbri, S; Offin, D G; Symonds, N; Kiang, K S; Knee, R J; Yoganantham, D C; Webb, J S; Birkin, P R; Leighton, T G; Stoodley, P Removal of dental biofilms with an ultrasonically activated water stream Journal of Dental Research, 2015, 94, 1,303–1,309

Chemistry New Boundaries | University of Southampton

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