CSCP Research News
Congratulations to Graham Sandford and his research group on receiving the 2018 AstraZeneca, GlaxoSmithKline (GSK), Pfizer and Syngenta Prize for Process Chemistry Research. This is the 13th time the annual prize has been awarded to a UK based academic who has developed chemistry that has the potential to be of relevance to large scale manufacturing. This national award was for research that could increase the availability of an effective treatment for a strain of meningitis in less developed countries. The work could see drugs for the treatment of Cryptococcal Meningitis (CM) become more readily available.
Professor Sandford said: “The technology and techniques we are developing at Durham can be used by industry and could have significant benefits in enhancing the use and application of fluorine gas. This award is for everyone who has worked on our fluorination research, including students, analytical support staff and for our successful knowledge transfer partnerships with industry.”
The Durham Fluorine Group developed a method of making flucytosine from a starting material of cytosine which is a readily available, naturally occurring product. The new technique - called continuous flow fluorination - continuously passes fluorine gas through a reactor tube, together with a solution of cytosine in acid. In the tube the fluorine gas reacts with the cytosine molecules to make flucytosine in a very controlled process. This method uses less energy, fewer raw materials and produces less waste than existing production processes and is also less expensive.
Research into new methods for manufacturing anti-fungal drugs is part of the commitment to health research overseen by Durham University’s Centre for Global Infectious Disease, which brings together specific, multidisciplinary expertise between the biological, chemical and physical sciences to tackle challenges in global infectious disease. Another process developed earlier by the Durham Fluorine Group – direct selective fluorination – is used by industry to produce chemical intermediates that are used in making the world’s top-selling anti-fungal drug, V-Fend® (Pfizer). V-Fend® is used to treat invasive pulmonary aspergillosis, a fungal infection of the lung, which is potentially fatal and develops mainly in people whose immune systems have been compromised by disease or cancer treatment.
The Durham Fluorine Group has collaborated in research programmes with a number of national and international industrial partners including Asahi Glass (Japan), F2 Chemicals, Pfizer, Murata Manufacturing Co. (Japan), Syngenta, AstraZeneca, Afton Chemical, SONY (Germany), GSK, Sanofi (France) and Mepi (France).
Laurent Pichon, President of Mepi, in Toulouse, France, said: “We are really proud to have been given the opportunity to work with Professor Graham Sandford and his team, throughout the flucytosine project. We were able to combine challenging process innovation available at MEPI, together with fluorine chemistry expertise developed by Durham University, to achieve fantastic results. Beside technical excellence, we shared an unrivalled human experience that will remain for long, and open the door to a new, efficient, and responsible medicine.”
Alain Rabion, expert in chemistry at Sanofi, France, said: “It has been a great opportunity for Sanofi to develop a very efficient and fruitful partnership with Professor Graham Sandford and his team in the framework of the European Community Innovative Medicines Initiative (IMI) project CHEM21 consortium. “Based on excellence with fluorine chemistry expertise developed by Durham University and thanks to knowledge transfer proposed by Graham and his team, it has been possible for Sanofi to study a new fluorination methodology based on the use of elemental Fluorine gas as electrophilic reagent and continuous process using flow conditions as technology (milli-reactor).This successful collaboration involving Durham University, Sanofi and MEPI ended up with a new, readily scalable method for the direct synthesis of Flucytosine from cytosine using fluorine gas, which is unquestionably a technical success.”
Dr Alan Steven, Associate Principal Scientist, AstraZeneca, said: “Graham’s progress and achievements in taming fluorine gas, particularly from a technology point of view, are starting to change the way process chemists go about incorporating a fluorine atom into a target molecule.”
January 2018Sergey Arkhipenko and Prof Andy Whiting recently published a paper entitled 'Mechanistic insights into boron-catalysed direct amidation reactions' in the high impact journal Chemical Science.
The generally accepted monoacyloxyboron mechanism of boron-catalysed direct amidation is brought into question in this study, and new alternatives are proposed. We have carried out a detailed investigation of boron-catalysed amidation reactions, through study of the interaction between amines/carboxylic acids and borinic acids, boronic acids and boric acid, and have isolated and characterised by NMR/X-ray crystallography many of the likely intermediates present in catalytic amidation reactions. Rapid reaction between amines and boron compounds was observed in all cases, and it is proposed that such boron-nitrogen interactions are highly likely to take place in catalytic amidation reactions. These studies also clearly show that borinic acids are not competent catalysts for amidation, as they either form unreactive amino-carboxylate complexes, or undergo protodeboronation to give boronic acids. It therefore seems that at least three free coordination sites on the boron atom are necessary for amidation catalysis to occur. However, these observations are not consistent with the currently accepted 'mechanism' for boron-mediated amidation reactions involving nucleophilic attack of an amine onto a monomeric acyloxyboron intermediate, and as a result of our observations and theroetical modelling, alternative proposed mechanisms are presented for boron-mediated amidation reactions. These are likely to proceed via the formation of a dimeric B-X-B motif (X=O, NR), which is uniquely able to provide activation of the carboxylic acid, whilst orchestrating the delivery of the amine nucleophile to the carbonyl group. Quantum mechanical calculations of catalytic cycles at the B3LYP+D3/Def2-TZVPP level (solvent = CH2Cl2) suppport the proposal of several closely related potential pathways for amidation, all of which are likely to be lower in energy than the currently accepted mechanism.
Jack Pike, PhD student in the Walton group, won a poster prize at the 2017 RSC Coordination and Organometallic Discussion Group meeting at Lancaster University. Jack’s poster “Ruthenium-Mediated Nucleophilic Trifluoromethylation of Arenes” was awarded the prize from a field of more than 30 posters. The work described a novel method for installing CF3 group into aromatic substrates, using organometallic Ru complexes. This work was recently published in Chem Commun (2017, 53, 9858) . Jack’s PhD work also led to a novel C-H activation reaction, which was published in Organometallics (2017, 36, 4376). Here’s a photograph of Jack with his award and Dr Nick Fletcher of Lancaster University.
Research between the Durham Fluorine group led by Graham Sandford and industrial collaborators Sanofi-Aventis and MEPI in France, funded by the European Union Innovative Medicines Initiative (IMI; www.imi.europa.eu) has led to a new, more efficient way of producing flucytosine (http://pubs.acs.org/doi/abs/10.1021/acs.oprd.6b00420), a WHO essential medicine (www.who.int/medicines/publications/essentialmedicines/en/) used to treat a common and often deadly fungal form of meningitis in people with HIV / AIDS.
Press releases from the IMI (http://www.imi.europa.eu/content/chem21-flucytosine) and the American Chemical Society (https://www.acs.org/content/acs/en/pressroom/presspacs/2017/acs-presspac-february-1-2017/cheaper-way-to-make-who-designated-essential-medicine.html) highlight the collaborative R&D project.
Patients with HIV / AIDS have weakened immune systems and so are particularly susceptible to fungal infections such as cryptococcal meningitis (CM). There are 950 000 cases of CM worldwide every year, and 625 000 deaths, making CM the leading fungal cause of death for people with HIV / AIDS. The majority of cases are in sub-Saharan Africa.
The recommended treatment for CM is a combination of flucytosine and another drug called amphotericin B, both of which feature in the World Health Organization (WHO) List of Essential Medicines. However, flucytosine is not registered for use in any African country and so cannot be prescribed as a treatment there. Flucytosine is also very expensive, as its patented manufacture involves carrying out a sequence of four chemical reactions.
The Durham method is expected to decrease costs of production, and so make the medicine more affordable for the many people with HIV/AIDS who live in low income countries. Graham and his PhD student Antal Harsanyi devised a way of making flucytosine via a one-step ‘continuous flow’ method that uses the readily-available natural product cytosine as its starting point. In this technique, fluorine gas is passed through a steel tube together with a solution of cytosine in acid and, in the tube, fluorine reacts with the cytosine molecules to make flucytosine. Because it involves just one selective reaction instead of four, the new method uses significantly less energy and raw materials and produces less waste than conventional techniques to manufacture flucytosine. The academic/industry team has carried out successful pilot-scale studies to help enable scale up to industrial production.
This operationally simple procedure from inexpensive starting materials offers the only alternative manufacturing procedure for flucytosine to the currently operated expensive four-step process. Hopefully, this one-step low cost synthesis of flucytosine will help to raise awareness of the neglected CM health epidemic and ultimately contribute to meeting the urgent requirement for large quantities of flucytosine for low income nations.
Simon Beaumont represented CSCP in a British Council Newton Research Links visit on the Rational Design of Catalysts to Indian Insititute of Technology Madras (in Chennai) and the National Centre for Catalysis Research based there.
Kate Madden (Whiting group) won a best poster at the RSS’s Applied Catalysis Group biannual meeting, ‘Challenges in Catalysis’ at Burlington House in London, November 2016.
Alba Pujol (Whiting group) presented a poster at the RSC’s Applied Catalysis Group biannual meeting, ‘Challenges in Catalysis’ at Burlington House in London, November 2016.
Paul McGonigal gave an invited seminar titled “Shapeshifting Cations and Functional Aromatics Made Easy by Gold Catalysis” at Dartmouth College, Hanover, New Hampshire, USA on 9th June. Jiří Šturala (postdoc in McGonigal Group) also gave an invited seminar on “Aggregation Induced Emission in Carbocyclic Materials” at the RSC Northern Chemistry Postdoctoral Meeting, Huddersfield University, UK on 10th June.
A study by Simon Beaumont and his PhD student, Laura Bingham, has just been published in the high-impact journal Nature Materials. The research reports the successful selective dual-functionalisation of porous materials with a high degree of spatial control over where each functionality is located (selectively to either large or small pores). The value of these new materials is demonstrated as unusually selective catalysts for an otherwise challenging one-pot oxidation of cinnamyl alcohol to cinnamic acid. paves the way for future, more energy efficient catalytic processes (able to make use of just one reactor for multiple reactions). In addition, possible applications are being considered in a plethora of other fields such as energy, health, information storage and communications. The work conducted at Durham is part of a collaborative research team comprising researchers at Aston and Leeds universities.
Andy Whiting gave three oral presentations on “Centre for Sustainable Chemical Processes”, “Flow chemistry and microfluidics at Durham” and “Fluorine chemistry capability and expertise at Durham”, and Li Li gave an oral presentation on “The ICRF: Integrated chemical reaction facility” at North East Innovation Showcase 2015, Durham University. This unique event held by the North East Process Industry Cluster aimed to bring industry together with the region’s five Universities to showcase process sector innovation and expertise and facilitate academic-industrial collaboration.
CSCP members Mark Fox and Andy Whiting worked with graduate student Duangduan Chaiyaveij (now lecturer in Organic Chemistry at Thammasat University in Thailand) to further develop their work on green, copper-catalysed air-based oxidations of hydroxamic acids, followed by trapping in situ with different dienes and have had their work recently published in the Journal of Organic Chemistry. The research involved DFT calculations in order to understand what parameters govern [4+2] versus ene-cycloaddition, and the effect of substituents upon the diene and dienophile components.
Alba Pujol (Andy Whiting group) presented a poster below at the NORSC meeting in York on the 23rd September 2015.
Congratulations to Laura Bingham (PhD student with Simon Beaumont) on winning a poster prize at the UK-wide RSC Surface Reactivity and Catalysis (SURCAT) meeting on the 18th September in London for a poster about her work on total internal reflection Raman of catalyst surfaces.
Tony Harsanyi (3rd year PhD student, Graham Sandford Fluorine Group) was awarded a poster prize (500 euro) sponsored by the German Chemical Industry group of the German Chemical society (GDCh) at the recent 21st International Symposium on Fluorine Chemistry, Como, Italy (www.fluorine-como2015.eu). The poster, titled ‘Synthesis of fluoromalonate esters: Assessment of the greenness of direct fluorination’, was selected from over 100 contributions.
David Hodgson gave an oral presentation on “N,S-Bridging Thiophosphoroamidates: Synthesis and Reactivity" at the ESOR 2015 conference, Kiel, Germany. He also successfully obtained a BBSRC grant, with Martin Cann and Martin Schröder (Biological Sciences) aso co-investigators, to carry out a study titled 'A Chemo-Enzymatic Approach Towards Gamma-Thio-Nucleoside-5'-Triphosphates'.
Phil Dyer spent a week in Germany visiting the universities of Marburg, Kassel, Wuerzberg, Bielefeld, and Goettingen where he presented five invited research talks entitled: "Innocent Until Proven Guilty - Responsive Organophosphorus Compounds”, “Understanding Catalytic Olefin Dimerisation”, “Bidentate Phosphine-Alkene Ligands: Electronically Flexible Metal Scaffolds"; his invited talk in Kassel was sponsored by the GDCh (the German Chemical Society).
AnnMarie O'Donoghue presented a poster in Durham Castle on May 18th 2015 at a 'Celebrating Excellence Symposium' on aspects of her research.
Kate Madden, a PhD student with Andy Whiting, won a poster prize at the RSC Medicinal Chemistry Residential School from 21st-26th June in Loughborough. Her poster is shown below.
Alba Pujol, PhD student with Andy Whiting, presented a poster below at the conference "Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS) 18", in Sitges (Catalonia, Spain) from the 28th June to 2nd July.
Dr Paul McGonigal took up the position of Lecturer in Organic Chemistry at Durham University in June, 2015. He received his undergraduate (MChem, 2007) and postgraduate (PhD, 2010) degrees from The University of Edinburgh, working under the direction of David Leigh. In 2011, he moved to The Institute of Chemical Research of Catalonia (ICIQ), Spain, as a Postdoctoral Researcher in the laboratory of Antonio Echavarren. The following year, he joined Fraser Stoddart’s research group at Northwestern University as a US–UK Fulbright Scholar.
Congratulations to Jaspreet Sanghera (PhD student with Phil Dyer) and David Tucker (PhD student with AnnMarie O'Donoghue) on winning poster prizes at the Durham Chemistry Postgraduate Symposium on 24th June.
David Hodgson, as a member pf the RSC's Nucleic Acids Group Committee, is co-chairing 'Nucleosides and Nucleotides: synthetic and biological chemistry' in London on 17th April 2015. For details click on Nucleosides at http://www.maggichurchouseevents.co.uk/bmcs/
Ezat Khosravi gave a talk at the Institute of Environmental Biotechnology, University of Natural Resources and Life Sciences, Vienna, Austria on 12-14 February 2015.
Congratulations to Prof Andy Whiting on his RSC Fellowship award (FRSC), Dr AnnMarie O'Donoghue on joining the RSC Organic Division Council and Dr Phil Dyer on joining the steering committee of the UK EPSRC Catalysis Hub.
Dr Phil Dyer organised the Ken Wade symposium with the aid of Dr Mark Fox at Durham on December 14-15th which was a success and a fitting tribute to Ken Wade. Serge Arkhipenko from Prof Andy Whiting's research group won the best poster (below) at the meeting. Serge also presented his poster at the 4th RSC / SCI symposium on Challenges in Catalysis for pharmaceuticals and fine chemicals on November 5th in London. It is based on a new idea of merging the principles of bifunctional catalysis and recently emergent "Frustrated Lewis Pairs" Chemistry.
Heidi Korhonen (Hodgson group) presented her work at the International Roundtable on Nucleosides, Nucleotides and Nucleic Acids in Poznan, Poland in August 2014 (http://www.irt2014.pl/about_poznan). Heidi also presented he work to the RSC’s Nucleic Acids Forum meeting in London in July.
David Hodgson visited Turku in Finland in November to deliver a series of medicinal chemistry lectures to undergraduates. David also delivered a research talk focusing on bioorganic phosphate chemistry. The Bioorganic group in Turku is one of the world’s leading groups focusing on the mechanisms of phosphate ester transfer (http://www.utu.fi/en/units/sci/units/chemistry/research/orgchem/bioorganic/Pages/home.aspx). David also presented Heidi's work at the International Conference on Phosphorus Chemistry in Dublin in June (abstract below, http://www.icpc2014.ie), and part of the work has now been accepted for publication in the ICPC meeting special issue of the journal Phosphorus, Sulfur, Silicon and the Related Elements (doi: 10.1080/10426507.2014.984032 ).
Graham Sandford and Steven Cobb are coordinating the Fluorine 21 International Training Network (ITN). Graham has realeased a FLUORINE21 ITN newsletter.
- F21 ITN newsletter (last modified: 5 December 2014)
Alba Pujol, a PhD student from Andy Whiting's group, presented a poster at the conference "Challenges in Catalysis symposium" in London on the 5th November, 2014.
Dr Li Li (ICRF manager) also presented a poster about Integrated Chemical Reaction Facility (ICRF) (poster below) at 4th NORSC PG Symposium on 23rd October 2014, Huddersfield University.
Farhana Khanam Ferdousi, a PhD student in the Whiting group, has presented a poster at the NORSC meeting in Huddersfield on the 4th November, 2014. Farhana is working on the sustainable processes for the direct amide bond formation and hopes this work will be one of the steps in developing future environmentally benign catalysts for the catalytic direct amide formation.
David Wong-Pascua and Oliver Maguire attended the 22nd IUPAC International Conference on Physical Organic Chemistry in Ottawa, Canada, on August 10th-15th. Oliver was one of very few PhD students who gave a talk at the meeting and David presented a poster. AnnMarie O'Donoghue and David Hodgson attended the STINT Summer School in Karolinska during September, which involves a taught series of workshops for the graduate students with each academic giving a two-hour taught workshop, along with PhD students Vicki Linthwaite, Oliver Maguire, David Wong-Pacua, David Tucker and PDRA Stefanie Freitag-Pohl.
AnnMarie gave an invited lecture in Japan in April at ISRIUM 2014 (International Symposium on Reactive Intermediates and Unusual Molecules) and have recently submitted a paper to a special issue of the Journal of Physical Organic Chemistry for all invited speakers. Congratulations to AnnMarie on receiving the 2014 RSC Loschmidt Award for Physical Organic Chemistry.
Niamh Ainsworth (a fellow Irish woman!) has just joined AnnMarie O'Donoghue/David Hodgson groups as a PhD student on an EU funded project. Peter Quinn (former Durham undergraduate) will join the same groups in January 2015.
Felicity and Chris Greenwell won £10k from the SUPERGEN Bioenergy Hub to conduct a “Feasibility study to assess how opinions and perspectives differ of anaerobic digestion (AD) bioenergy between intra- and inter-community stakeholder groups of a well-received versus a controversial AD plant.”
Jack Rowbotham (PhD student with Phil Dyer/Chris Greenwell) attended the 17th Brazilian Meeting of Inorganic Chemistry (BMIC), held in Araxá, Brazil from 10th-14th August. BMIC is the principle meeting of the inorganic division of the Brazilian Chemical Society and was attended by chemists from across South America and around the globe. Jack was one of a group of delegates attending the meeting as a representative of the Royal Society of Chemistry Dalton Division and was invited to give an oral presentation at the conference. His presentation entitled “Opening the Egg-Box: seaweed-derived sugars as ligands in the coordination of s-block metal ions” focussed on the interactions between alginic acid and s-block metal ions. This work forms part of Jack’s wider project exploring the thermochemical treatment of kelps. Jack really enjoyed the conference and was grateful of the opportunity to discuss many aspects of inorganic chemistry in the beautiful Brazilian countryside.
CSCP PhD student Adam Calow has completed a fundamental study to understand what controls 1,2- versus 1,4-addition of amines to unsaturated aldehydes and ketones, using a combination of ReactIR and NMR. This study has been supported by theoretical studies with collaborators at Taragonna, which has highlighted the role of major enone-enal conformation on the reaction outcome.
The work has been published in Journal of Organic Chemistry:
Luke Tuxworth (CSCP PhD student in Phil Dyer's group) celebrated his graduation this month, following defence of his PhD entitled "Novel P-Alkene and POCOP Ligands: Synthesis, Coordination Chemistry, and Reactivity". Luke is now a research scientist working with Johnson Matthey Catalysts in Billingham. Congratulations Luke! Some of Luke's work has recently appeared as a full paper in a Themed Collection "Synergy Between Experiment and Theory" featured in Dalton Trans.:
"Combined DFT and experimental studies of C–C and C–X elimination reactions promoted by a chelating phosphine-alkene ligand: the key role of penta-coordinate PdII", L. Estévez, L. W. Tuxworth, J.-M. Sotiropoulos, P. W. Dyer and K. Miqueu, Dalton Trans., 2014, 43, 11165-11179 DOI: 10.1039/C4DT00340C
Third year CSCP PhD Student, Adam Calow (Whiting group), has just had a paper accepted in Organic and Biomolecular Chemistry which reports total synthesis of Fluoxetine (Prozac) and Duloxetine (Cymbalta). These are top-selling pharmaceuticals used for the treatment of depression and other conditions. This work showcases some of the advancements made by the Whiting-Fernández group collaboration in the area of asymmetric β-borylation and, in particular, β-borylation of α,β-unsaturated imines.
James Radcliffe (final year of his PhD with Phil Dyer and funded by Sasol UK) is presenting some of his research (poster below) at the XXVI International Conference on Organometallic Chemistry in Sapora, Japan (July 2014).
Farhana Ferdousi (Andrew Whiting) gave a presentation at the 247th ACS National Meeting - Division of Catalysis Science and Technology, March 16-20, 2014, Dallas, Texas
“Novel approaches towards green catalytic direct amide bond formation”
The significance of amides as a component of biomolecules and synthetic products has triggered the development of catalytic direct amidation methods 1,2,3 which involve reaction of a carboxylic acid and amine to form an amide with water as the only by-product. These methods evade the need for stoichiometric activation or coupling reagents and hence, are important green chemical processes 1,2. The present study involved the development a mild reaction conditions for the direct amidation reaction where known arylboronic acid catalysts 1,2,3,4,5 were employed in two different model reactions and compared with both reported 6,7 and potential organometallic catalysts (Zr and Fe based).
After a systematic evaluation of solvent, temperature and catalyst, ambient reaction conditions were applied in the direct amidation of amino-acid derivatives in order to exploit these more economical reagents for peptide synthesis. Protected amino acid derivatives showed slow reactivity compared to simple amine-carboxylic acid combinations though did proceed at 65~68 °C generally avoiding racemization.
3,4,5-Trifluorophenylboronic acid and o-nitrophenylboronic acid were found to be the best catalysts, though for this sluggish reaction, high catalyst loadings were required. However, an interesting synergistic catalytic effect was observed during dipeptide formation using ‘Co-Catalyst’ (mixture of o-nitrophenyl boronic acid and o-methylphenylboronic acid (1:1)) in the direct amidation reaction at lower temperatures, although the process was particularly slow. Driven by this impressive result, the effect of cooperative catalysts, particularly, on the less reactive acid-amine combination (which was found to be inert at low temperature with single catalysts) was tried to explore. As a consequence, some commercially important synthesis has been reviewed through this novel cooperative catalysis to ensure their real applicability in industries.
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A new perspective article in Phys. Chem. Chem. Phys on Nanomaterials in Fischer-Tropsch chemistry by Simon Beaumont has appeared online:
A recent paper from the CSCP, entitled "A selective transformation of enals into chiral gamma-amino alcohols," recently published in Organic Letters (by A. D. J. Calow, A. S. Batsanov, A. Pujol, C. Solé, E. Fernández and A. Whiting, 2013, 15, 4810-4813, DOI: 10.1021/ol4022029) has been highlighted in SynFacts by authors M. Lautens, M. Sickert (see SynFacts, 2013, 9, 1306, DOI: 10.1055/s-0033-1340143).
AnnMarie O’Donoghue’s J. Am. Chem. Soc. publication (2012 134, 20421–20432) was chosen as a highlight in a JACS Spotlight issue: J. Am. Chem. Soc., 2013, 135 (4), 1165–1166.
Prof Andy Whiting gave a keynote lecture and Adam Calow gave a talk at Euroboron 6 in Poland. Here are their abstracts.
Jack Rowbotham (PhD student jointly working between the Dyer+Greenwell groups in Chemistry) co-funded by DEI and CPI, has been awarded a Royal Society of Chemistry Westminster Fellowship. This award enables the recipient to work for three months in the Parliamentary Office of Science and Technology (POST) with the responsibility of keeping members of both houses of parliament informed on matters of current scientific importance.
Jack will take part in the writing of concise, peer reviewed reports (POSTnotes) as well as providing technical assistance to relevant select committees as they go about their enquiries.
A grant of €3.3 m was awarded to the EU ITN Network (approx. €750k to Durham) coordinated by the Durham team of Graham Sandford and Steven Cobb with 6 academic partners (Prague, Berlin, St Andrews, Dublin, Munster, Neuchatel) and 4 industrial partners (AstraZeneca, Bruker, Almac, F2 Chemicals) entitled ‘FLUOR21 : Synthesis, structure and function of fluorinated systems’ training a cohort of 12 young researchers over a 48 month period.
Garr-Layy Zhou presented a poster at the 43rd National Organic Chemistry Symposium, University of Washington in Seattle on Wednesday 26th June 2013.
Andy Whiting and Mark Fox, in collaboration with co-workers in Rennes, reported a novel route to N-arylpyridines from boronodienes and arylnitroso compounds in a Chem. Commun. article. Animations on the steps involved in the reaction mechanism can be viewed with the powerpoint file, Tripoteau.ppt.
The University together with Dr John Birtill - supported by Andy Whiting, the RSC’s Applied Catalysis Group and the SURCAT Group - organised and hosted a commemorative symposium “Catalysis – from fundamentals to application” for the late Dennis Dowden who was a distinguished senior scientist for many years at ICI Billingham. The meeting was sponsored by Johnson Matthey. This successful event attracted around 120 delegates from both academia and industry with 15 talks covering a wide spectrum of industrially-orientated catalysis, including talks from Martyn Twigg (CSCP advisory board) “Dennis A Dowden – An appreciation of a life in catalysis” and from Martin Hanton (PWD’s first PhD student now working with Sasol Technology UK) titled “Selective ethylene tetramerisation 2003-2013 – from discovery to commercialisation”. James took the opportunity to again present some of his work at the poster session on the first evening: “Catalysis using PNE Complexes of Group VI Metals”.
Jack Rowbotham (PWD and HCG) attended the Royal Society of Chemistry’s Thermal Methods group, Thermal Analysis Conference TAC 2013, held at the University of Greenwich and presented a poster detailing some of his recent working on understanding the thermolysis of seaweed-derived sugars and the key roles played by metals. Jack also attended the group’s short course on Thermal Analysis Techniques – An Overview. This provided a comprehensive overview of the main thermal analysis techniques including DSC, TG, TMA, DMA and evolved gas analysis and their industrial applications.
Professor Michael K Theodorou awarded Visiting Chair
Prof. Mike Theodorou has recently been awarded a visiting chair in the Chemistry Department at Durham University in conjunction with the Department's Centre for Sustainable Chemical Processes (CSCP).
Mike is recognised internationally for his pioneering studies on gut anaerobic fungi and the role of plant biomass, including high sugar grasses, in rumen function and in a number of collaborative projects, has developed and patented continuous culture technologies for microbial cell growth and biogas production - converting organic waste and biomass into gaseous biofuel.
Mike holds a PhD in Biochemical Plant Pathology from Imperial College London and a BSc in Microbiology from the University of London. His career in strategic and applied research is in the area of anaerobic microbiology/microbial ecology and includes 12 years as department head at the Institute of Grassland and Environmental Research (IGER), Aberystwyth, and as head of Science Development at Aberystwyth University. More recently, Mike spent 2 years in Biological and Biomedical Science at Durham as a Visiting Professor in Industrial Biotechnology. This post was part-sponsored by the Centre for Process Innovation (CPI); a Technology Strategy Board Catapult Centre. He is currently collaborating with the Broad Institute of MIT and Harvard and theUniversity of California, Santa Barbara (UCSB) on a project aimed at the industrial exploitation of the gut fungi. Simultaneously, Mike is currently employed as a consultant by the Technology Strategy Board where he is engaged in contributing to the commercialisation of novel, advanced manufacturing technology in the food/feed industry and in recommending technical and scientific inputs to science-based business.
With colleagues at Durham and Silage Solutions Ltd, Mike recently developed a novel, patented process for macroalgae preservation. This process enables macroalgae to be stored for considerable periods (more than a year) without noticeable deterioration making the preserved algal biomass an innovative, sustainable source to permit continuity of supply as an intermediate energy carrier for biofuel production. In 2013, the Chemistry Department was awarded £2.4 M by the EPSRC for a 5-year collaborative project (MacroBioCrude) to exploit Mike’s macroalgae preservation process. The project is led by Phil Dyer in Chemistry and sets out to demonstrate an ambitious, industrially viable, novel, integrated and economic supply and processing pipeline for year-round sustained production of fuel-specification hydrocarbons (drop-in replacement diesel and aviation kerosene) from preserved macroalgae and to investigate societal, and industry acceptability of the proposed chain.
Jack Rowbotham, Li Li and PWD attended the international SubiCat meeting “Sustainable Catalytic Conversions of Renewable Substrates” held in St. Andrews. Both Jack and Li Li presented some aspects of their research work with posters entitled “Seaweed and sustainability: exploring the catalytic pyrolysis of macroalgae as a route to renewable fuels and chemicals” and “Sustainable Bio-Derived Ketones via Heterogeneous Catalysed Fatty Acid Deoxygenation Reactions”, respectively. In an invited talk, PWD presented some of the work carried out jointly with Chris Greenwell (HCG)’s group in the areas of heterogeneously-catalysed ketonic decarboxylation and trans-esterification “Moulding biomass with clays and mixed metal oxides”.
Dr Chris Greenwell has been awarded a Royal Society Industry Fellowship to understand how clay minerals and clay mineral/other mineral interfaces hydrate during drilling and fracking operations. The Fellowship will last for 4 years and Chris will spend 50% of his time working with M-I SWACO (Schlumberger) on the project, making use of the world class Aberdeen Research & Technology Centre.
Congratulations to Simon Beaumont was awarded EPSRC support for his ‘CataRaman’ project under the EPSRC First Grant scheme. The project will be focused on exploiting Total Internal Reflection (TIR) Raman spectroscopy for in situ studies of heterogeneous catalysis. This methodology, which offers a number of advantages over current alternatives, will be exploited for the first time to study reactive adsorbates under true operating conditions on specially prepared, well defined nanoparticle catalysts.
Congratulations to Graham Sandford who was elected Chair of RSC Fluorine Chemistry Group (2013-17). This appointment was highlighted in the German magazine ‘Spektrum’.
Graham was also guest editor for a special issue of J. Fluorine Chem. (Editorial, November 2012)
Jack attended the RSC Energy & Environment - Early Career Researcher Symposium, at Cranfield University, where he won 2nd prize in the meeting's poster session. His poster, entitled "Seaweed and Sustainability: Biofuels from the Catalytic Pyrolysis of Macroalgae", describes Jack's recent work exploring fundamental aspects of the pyrolysis of macroalgae - a methodology that could be used to generate fuels and chemicals from this sustainable bioresource.
This study includes a thorough kinetic analysis of the thermochemistry of real macroalgal samples together with that of model compounds such as alginic acid. Importantly, Jack's work highlights the significant impact of metals in these types of thermochemical process, something extremely important since macroalgae naturally bioaccumulate metal ions to concentrations many thousands of times higher than their surroundings. Jack has demonstrated that the presence of these metals dramatically affects the the kinetics of their pyrolysis and has shown that different metal ions impact quite differently. Again, Jack has supported this study with investigations of the thermochemistry of a range of metal alginate salts. Together these results highlight the potential for undertaking catalytic pyrolysis of seaweed to generate useful, up-graded commodity chemicals in a concise reaction slate. Further details of Jack's work in this area will appear in a special edition of Journal of the Royal Society Interface, later this year:
"Copper(II)–mediated thermolysis of alginates: A model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae",
J. S. Rowbotham, P. W. Dyer, H. C. Greenwell, D. Selby, M. K. Theodorou, Interface Focus, 2013, 3; doi:10.1098/rsfs.2012.0046
This is great result for Jack - coming as the third presentation prize he has won at a national meeting this year!
The MacroBioCrude consortium lead by Phil Dyer (Centre for Sustainable Chemical Processes, Durham Chemistry, and Royal Society Industry Fellow) supported by Mike Theodorou has received EPSRC funding (£1.6M) to support a cross-discipline project to establish an integrated supply and processing pipeline for the sustainable manufacture of liquid hydrocarbon fuels from seaweed (or macroalgae).<span >MacroBioCrude brings together both researchers from five universities, Durham (Chris Greenwell - Earth Sciences; Victoria Wells - Business School), Aberystwyth (Joe Gallagher - Institute of Biological, Environmental and Rural Studies), Swansea (Robin Shields - Centre for Sustainable Aquaculture Research), Greenwhich (Pat Harvey, Bioenergy/Life Sciences) and Highlands and Islands (Alan Bourhill - Marine Science and Technology), as well as industrial partners Johnson Matthey Catalysts, Davy Process Technology, Silage Solutions Ltd, Shell, CPI and CPI/Tata Steel. The team will explore methods of seaweed gasification and upgrading to diesel and aviation kerosene employing a novel biomass preservation technology developed by members of the consortium. In parallel, they will establish an innovation platform for this novel bio-fuel supply chain, which assesses the overall process footprint, supply chain relationships and public/end-user perceptions. Seaweed makes an ideal sustainable feedstock to contribute to the manufacture of high energy density liquid transport fuels since it does not compete with foodcrops for land or water, has a rapid growth cycle combined with a high solar efficiency (~3 times greater than terrestrial biomass), and can be grown alongside other water-based activities such as off-shore wind farms and fish farms.The consortium was initially formed via the IAS Biofuels, Science and Society theme and is a great example of Durham interdisciplinary work and the role the IAS can play in stimulating this.
For more information on the successful EPSRC grant see http://www.epsrc.ac.uk/newsevents/news/2013/Pages/newresearch.aspx
More information on using seaweed as a sustainable feedstock can be found in a recent article "Thermochemical processing of macroalgae: a late bloomer in the development of third-generation biofuels?" by Phil Dyer, Chris Greenwell, Mike Theodorou and Jack Rowbotham at http://www.future-science.com/doi/abs/10.4155/bfs.12.29
Dr Chris Greenwell gave an invited talk, "Deoxygenation Reactions in Biomass Conversion" to the US National Renewable Energy Laboratory (NREL) in Golden, Colorado on Friday 30th September. The talk was very well received and Dr Greenwell stayed on for a briefing by the Bioenergy Programme Manager to NREL on the current status and prospects for bioenergy.
In a collaborative research group effort involving undergraduate project students, PhD students and postdocs, Luke Tuxworth, Lise Baiget, Andreas Phanopoulos, Owen Metters, and Phil Dyer publish a paper in Chem. Commun. “Phosphine–alkene ligand-mediated alkyl–alkyl and alkyl–halide elimination processes from palladium(II)” describing their work in the area of ‘responsive’ ligands. This article can be found at: http://pubs.rsc.org/en/Content/ArticleLanding/2012/CC/C2CC35623F
Antonis Messinis, currently in the final year of his PhD working in Phil Dyer’s group on a Sasol UK funded project, presented a poster on aspects of his research entitled “Exploring Aspects of Tungsten-Initiated Olefin Dimerisation” at the XXV International Conference on Organometallic Chemistry Conference (ICOMC) in Lisbon, Portugal.
Phil Dyer’s group also took part in this year’s Royal Society of Chemistry Dalton Division Main Group Chemistry meeting held at Burlington House in London. Phil gave an invited lecture titled “Exploring the thermal behaviour and catalytic performance of main group synthetic clays and mixed metal oxides”, describing work his group are undertaking in collaboration with Chris Greenwell and Johnson Matthey. Luke Tuxworth (2nd year PhD student) also presented a snapshot of some of his on-going research in a poster describing “Phosphine-alkene ligand-mediated alkyl-alkyl and alkyl-halide elimination processes from palladium(II)”. After the meeting they managed to find time for a “few” beers and some very “tasty” sandwiches.
CSCP welcomes Prof. Ian Baxendale to Durham Chemistry and CSCP! Ian’s research interests include organic synthesis (natural products, heterocyclic and medicinal chemistry), organometallic chemistry, catalyst design and application, meso flow chemistry, microfluidics, microwave-assisted synthesis, solid supported reagents and scavengers, and facilitated reaction optimisation using robotics and automation.
Dr Li Li and Jack Rowbotham working jointly between the groups of Phil Dyer and Chris Greenwell publish a book chapter “An Introduction to Pyrolysis and Catalytic Pyrolysis: Versatile Techniques for Biomass Conversion”, which will appear in early 2013.
Andy Whiting and collaborators won a £897k award from the TSB. The 3 year project involves AkzoNobel, High Force Research, and Manchester University, and is aimed at investigating novel routes for the manufacture of waterborne polymers for coating applications. The major thrust of the project is the replacement of solvents and the use of more efficient continuous manufacturing processes to improve air quality and reduce greenhouse gases, thereby making coating manufacturing more sustainable.
In a major development it has been announced that Durham University has awarded £1.1M to CSCP to establish a new dedicated Integrated Chemical Reaction Facility (ICRF) within Durham’s Chemistry Department. The unique facility will provide academic and industrial researchers access to complex chemical process reactor systems and associated analytical instruments enabling unique high pressure, flow and parallel reactions supported by the provision of analytical instrumentation and process control systems. The ICRF will enhance and promote on-going research in homo- and hetero-genous catalysis, fluorine, flow, parallel and sustainable chemistries and will provide the capability for research in CO2 geochemistry, coal gasification, polymer pyrrolysis, biofuel synthesis, all with an emphasis upon engendering energy-efficient processes design and implementation.
The next NORSC research day event will show case the expansion of this research network to include researchers from the Universities of Hull, Huddersfield, Liverpool, Manchester and Sheffield. This event will take place on Wednesday 17th October at Kings Manor in York. It will provide an opportunity for each university to give a general presentation of their core research themes, areas for future collaboration and research directions. The programme will include talks from both research group leaders and PhD students, and a poster session.
Jack Rowbotham, Phil Dyer, Chris Greenwell and Mike Theodorou have jointly published a perspective article in the journal Biofuels, entitled “Thermochemical processing of macroalgae: a late bloomer in the development of third-generation biofuels?”. The paper offers a critical overview of the recent developments in thermochemical processing of macroalgae, a field that has been comparatively neglected when viewed against the vast wealth of research into alternative biofuel production methods and feedstocks. However, advances in thermochemical techniques have led to a flurry of activity into the applicability and use of macroalgae. Recent research has demonstrated that macroalgae may be used to produce bioresources in a similar way to many conventional terrestrial feedstocks and, indeed, may also possess a number of advantages (notably by not competing for land that could be used for food and forestry, nor requiring extensive use of nitrogenous fertilizers). With this in mind, it is suggested that many of the criticisms that have led to previous disinterest in thermal processing of macroalgae are not valid. Nevertheless, only through the continuation of these recent endeavors can macroalgal biomass, via broader and successively larger scale experimentation, demonstrate itself to be a competitive source of renewable energy. The full article can be found at: http://www.future-science.com/toc/bfs/3/4.
Andy Whiting and Chris Greenwell have jointly been awarded two METRC grants to work on collaborative ‘kick-off’ projects with Sun Chemicals on VOC-free crosslinked coatings, and on clay-nanocomposite barrier coatings. Chris has also been awarded a further METRC grant to work in collaboration with Dr Dave Davis (Silage Solutions Ltd) in order to undertake analysis of macroalgae carbohydrates as function of preservation methodology! This latter work will be undertaken by Catherine Ainsworth, recently graduated from Cambridge University.
Prof. Alois Fürstner (Max-Planck-Institut für Kohlenforschung) gave this year’s Musgrave Lecture entitled “Catalysis for total synthesis”. This formed part of an exciting half-day mini-symposium with accompanying lectures being presented by CSCP’s AnnMarie O’Donoghue and Dr Paul Davies (Birmingham).
This year the Chemistry Department in Durham was represented at the Science Faculty Rising Stars symposium (http://www.dur.ac.uk/science.faculty/symposium/) by Owen Metters who gave an excellent talk entitled “It’s Make or Break for the Chemical Bon”, which described research work he undertook during his final year M.Chem. research project with Phil Dyer and his group. Owen described his work surrounding the synthesis, coordination chemistry, and potential catalytic application of innovate bidentate phosphine-alkene ligands and how this unusual electronic asymmetry facilities key reductive elimination processes. Owen also presented this work at this year’s SCI Young Chemists Symposium held in Durham Chemistry.
David Hodgson has been invited to talk at XX IRT – the 20th International Roundtable on Nucleosides, Nucleotides and Nucleic Acids in Montreal (5-9 August 2012). Almost 100 "oral" category abstracts were received, but only 15 were selected by the programme committee. Additionally, David has been awarded an RSC Journals Grants for International Authors bursary to enable him to set up a collaboration with Dr Subha R. Das at Carnegie Mellon University in Pittsburgh. The work will focus on new strategies for RNA ligation.
Research undertaken Richard Delley, a 3rd year PhD student working with AnnMarie O'Donoghue and David Hodgson, on the hydrolysis of reactive phosphorus(V) chlorides has just been published in the Journal of Organic Chemistry: http://pubs.acs.org/doi/abs/10.1021/jo300808m. The work shows that phosphodichloridate and thiophosphodichloridate ions both show a remarkable lack of reactivity towards hydroxide ions thus they can be used under conditions of relatively high pH without adverse effects.
New Research Initiative
CompactGTL together with Durham University's EPSRC KTS programme have recently announced a collaborative research project lead by Phil Dyer to explore fundamental aspects of the operation of heterogeneous Fischer-Tropsch catalysts.
Inaugural NORSC-NEPIC Innovation Day
The first of what is hoped to be an annual meeting organised by NEPIC was held on the 24th April at Ramside Hall Hotel (Durham), which successfully brought together around 60 participants including researchers from Leeds, York, Newcastle, and Durham Universities, who are all active participants of the NORSC (Northern Sustainable Chemistry) cluster, alongside with industrialists from a range of companies and organisations. The aim of the event was to showcase the breadth of technical and scientific progress that is being made in sustainable technologies at these Northern Universities and the capabilities that exist, collectively, to support regional technology needs in the areas of sustainable chemical businesses and processes, with a view to developing and delivering a lower carbon future. Copies of all the presentations given will be available soon via the NEPIC web site; the presentation overviewing the activities and capabilities of Durham Chemistry's CSCP may be found here.
Alba Pujol, PhD student with Andy Whiting, presented a poster below at the conference "Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS) 18", in Sitges (Catalonia, Spain) from the 28th June to 2nd July.