rsc macrocyclic & supramolecular chemistry …...rsc macrocyclic & supramolecular chemistry...
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RSC Macrocyclic &
Supramolecular Chemistry Meeting 2015
Durham University
21st and 22nd December 2015
MASC 2015 has been made possible by the generous support of our sponsors
MASC 2015
Durham University
21st and 22nd December 2015
Welcome Welcome to the Royal Society of Chemistry Macrocyclic and Supramolecular Chemistry Group meeting 2015! We’re delighted to welcome you to Historic Durham and hope you enjoy the fabled North-eastern weather here in December. MASC2015 is taking place will take place on the Science Site of Durham University 21st and 22nd December 2015. The conference dinner will take place on the evening of Monday 21st December at the Historic Durham Castle the founding college of Durham University. Durham City is home to one of the most recognisable landmarks in the UK, the majestic Durham Cathedral. Together with adjacent Durham Castle, this UNESCO World Heritage Site forms one of the most stunning city panoramas in Europe. – See more at http://www.thisisdurham.com. We could not run this meeting without the hugely generous support of our sponsors listed on the inside front cover. THANK YOU ALL! They have made the conference possible, so please do visit them in our exhibition adjacent to the lecture theatre and show your gratitude for keeping costs low at this fantastic event. We are also greatly appreciative of the staff and students at Durham University who have helped make the event happen. We hope you enjoy MASC 2015.
Meeting Information Registration is in the reception area of the Calman Learning Centre (see map on back cover). Lectures will be on the ground floor in the Arnold Wolfendale Theatre (CLC013). Refreshments, lunches, posters and the exhibition are all on the second floor of the Earth Sciences Building directly adjacent to the Calman Centre on its left. This is a main conference space and comprises two large linked areas ES228/229 and ES230/231. Posters, exhibitions and refreshments will be split between the two spaces. The exhibition space is accessed either by lift or by stairs. Please follow the signs. We would be grateful if poster exhibitors could put up their posters as soon as they can in order to allow people to more time to read them during breaks. The conference dinner will take place in the historic Durham Castle off Palace Green (see map). The dinner starts at 7.30 pm on the Monday evening, with drinks served from 7 pm. The castle is ca. 10 minutes’ walk from the conference in the direction of the city centre.
Prize Draw Conference packs contain a sheet for collecting stamps from our exhibitors. If you can collect 10 stamps you are eligible to enter the prize draw to win an outstanding mystery prize. The winner will be announced at the closing ceremony.
Local Information The Calman Learning Centre at the Science site of Durham University (DH1 3LE) is located at the edge of Durham city centre. The Castle is situated in the middle of the city adjacent to the cathedral off Palace Green (DH1 3RN). For detailed information see http://dur .ac.uk/map. Durham railway station is 20 minutes’ walk from the conference venue and is situated on the east Coast main line. Taxis are available from many companies including Paddy’s 0191 3866662 and Polly’s 07910 179397.
Fire and Security information In case of a fire alarm in either building please leave in an orderly fashion and assemble in front of the Calman Learning Centre. In case of emergency on campus, please dial security on 0191 334 3333 (internal extension 43333).
Internet Access UK delegates should use the Eduroam wireless internet service. For details on using Eduroam please see: https://www.dur.ac.uk/cis/network/eduroam/ Individual accounts are available for those not on Eduroam. Please ask at the registration desk.
Twitter We encourage delegates to tweet using the hashtag #MASC2015.
Bob Hay Lecture The group award lecture is given in memory of Professor Bob Hay, one of the pioneers of macrocyclic chemistry in the UK. This prestigious lecture is given annually by a younger chemist working in the area of macrocyclic and/or supramolecular chemistry in its widest sense. The winner, Prof. Dave Adams (Liverpool) will presents the Bob Hay lecture at MASC2015 and retains the Bob Hay trophy donated by Bob’s family to celebrate his life and work in macrocyclic chemistry.
Robert Walker Hay was born in Stirling in 1934 and spent his early childhood there before his family moved to England. He attended Bolton Grammar School where, it should be noted, Professor Sir Harold Kroto was also a pupil at that time. He then went to Glasgow University to study for his BSc and PhD degrees in chemistry, graduating PhD in 1959 in carbohydrate chemistry. Following a brief period in industry, Bob took up his first academic appointment in New Zealand at the Victoria University of Wellington where he taught both organic and inorganic chemistry. However, it was for his work with Neil Curtis, carrying out some of the earliest experiments on self-assembly reactions, that he will be remembered. The Curtis-Hay tetraaza macrocyclic ligands, involving simple condensations of diamines with acetone, were some of the first such systems to be prepared. In 1971, Bob returned with his family to the UK to take up an appointment as reader in chemistry at the new Stirling University where he was made a full professor in 1986 and in 1988 Bob transferred to St Andrews. Throughout his career he retained an interest in biomimetic chemistry. Despite working with a group of never more than three or four people, he was principal author of more than 220 primary research papers, book chapters, and books. In 1994 he was instrumental in setting up, under the auspices of the Royal Society of Chemistry, the first discussion group in Europe devoted to coordination chemistry. He also had a long association with the RSC inorganic reaction mechanisms discussion group having served as a secretary and chairman and having been present at every meeting of the group since 1972 until his death. Bob was instrumental in bringing the International Symposium on Macrocyclic Chemistry to St Andrews in July 2000 and the meeting has since teamed up with MASC (Brighton 2012 and Cambridge 2017).
Previous winners: 2014 – Oren Scherman (Cambridge) 2013 – Jonathan R. Nitschke (Cambridge) 2012 – Andrew J Wilson (Leeds) 2011 – Lee Cronin (Glasgow) 2010 – David Smith (York) 2009 – Stephen Faulkner (Oxford) 2008 – Jonathan W. Steed (Durham)
2007 – James H. R. Tucker (Birmingham) 2006 – Thorfinnur Gunnlaugsson (Trinity College Dublin) 2005 – Neil R. Champness (Nottingham) 2004 – Philip A. Gale (Southampton) 2003 – Harry L. Anderson (Oxford) 2002 – Michael J. Hannon (Birmingham) 2001 – Michael D. Ward (Sheffield)
Programme - Monday 21st December 09.00 REGISTRATION in the Calman Centre Coffee is available in the Exhibition spaces on the second floor of the adjacent Earth Sciences building ES228 and ES230 10.20 – 10.30 OPENING ADDRESS Chair: Dr. Katharina Edkins 10.30 – 11.10 PLENARY LECTURE 1 Halogen-Bonded Soft Matter Prof. Pierangelo Metrangolo (Politecnico di Milano) 11.10 – 11.20 FLASH TALK 1 Good, Better, Best! Limiting Superfluous Ionophore Functionality Maximizes Effectiveness of a Potentio-static Sensor for Creatinine Louis Adriaenssens (University of Lincoln) 11.20 – 11.30 FLASH TALK 2 Homo- and Hetero-Circuit [3]Rotaxane Formation in the Bipyridine-Mediated AT-CuAAC Reaction Edward Neal (Queen Mary University of London) 11.30 – 11.55 INVITED LECTURE 1 Structural flexibility in the solid state Prof. Leonard J. Barbour (Stellenbsoch University) 11.55 – 12.20 INVITED LECTURE 2 Supramolecular routes to DNA-based Nanomaterials Prof. Andrew Houlton (Newcastle University) 12.20 – 12.35 INDUSTRIAL TALK 1 Advances in X-ray Crystallography Dr. Marcus Winter (Rigaku Inc.) 12.35 – 13.35 LUNCH ES228/229 and ES230/231 There are posters and exhibitions in both spaces. Please take this opportunity to talk to all the exhibitions in both sections. Exhibitors will stamp your collection card for the prize draw. Chair: Prof. Jim Tucker 13.35 – 13.45 FLASH TALK 3 Imposing control on self-assembly: rational design and synthesis of a mixed-metal, mixed-ligand coordination cage containing four types of component Alexander Metherell (Sheffield University) 13.45 – 14.10 INVITED LECTURE 3 Molecular cages in solution... or in nanomaterials? Dr. Valeria Amendola (University of Pavia)
14.10 – 14.35 INVITED LECTURE 4 Upper-rim Functionalisation of Calixarenes Including Inherently Chiral Racemic ABCD Calix[4]arenes Dr. Sean Bew (University of East Anglia) 14.35 – 15.00 INVITED LECTURE 5 Calixarenes: From cluster formation to directed assembly Dr. Scott Dalgarno (Heriot Watt University) 15.00 – 15.40 BOB HAY LECTURE Controlling Multicomponent Dipeptide Hydrogels Prof. Dave Adams (Liverpool University) 15.40 – 18.00 POSTER SESSION, RECEPTION, EXHIBITION ES228/229 and ES230/231. There are posters and exhibitions in both spaces. Please take this opportunity to talk to all the sponsors in both sections. Exhibitors will stamp your collection card for the prize draw. Sponsored by Perkin Elmer and Wiley Books. 19.00 for 19.30 CONFERENCE DINNER, DURHAM CASTLE Bar until midnight. Supramolecular Fun Casino in West Courtyard sponsored by Biopharma.
Programme - Tuesday 22nd December
Chair: Prof. Thorri Gunnlaugsson 09.00 – 09.40 PLENARY LECTURE 2 Molecular tectonics: from molecules to crystal welding Prof. M. Wais Hosseini (University of Strasbourg) 09.40 – 09.50 FLASH TALK 4 Detection of potassium ions with crown-ether appended lanthanide complexes Anne Junker (University of Copenhagen) 09.50 – 10.00 FLASH TALK 5 Self-assembly path of amyloidogenic peptides incorporating halogen-bond donor groups Luisa Lascialfari (Politecnico di Milano) 10.00 – 10.10 FLASH TALK 6 Nanoscale SAMul heparin binders as promising clinical tools Ana C. Rodrigo (York) 10.10 – 10.25 INDUSTRIAL TALK 2 Highlighting innovative solutions for the integration of parallel evaporation with other Chemistry tools in the laboratory Ian Bailey (Biopharma) 10.25 – 11.00 COFFEE BREAK ES228/229 and ES230/231 There are posters and exhibitions in both spaces. Please take this opportunity to talk to all the sponsors in both sections. Exhibitors will stamp your collection card for the prize draw.
Chair: Prof. Leonard J. Barbour 11.00 – 11.40 PLENARY LECTURE 3 Sponsored by Chem Development of supramolecular self-assembly architectures and materials Prof. Thorri Gunnlaugsson (Trinity College Dublin) 11.40 – 12.05 INVITED LECTURE 6 Sensing a Bacillis Anthracis Biomarker with well-known OLED Emitter EuTta3Phen Dr. Barry Blight (University of Kent) 12.05 – 12.30 INVITED LECTURE 7 Guest sequestration, packing, and folding within water-soluble nano-capsules Prof. Bruce C. Gibb (Tulane University) 12.30 – 13.30 LUNCH ES228/229 and ES230/231 There are posters and exhibitions in both spaces. Please take this opportunity to talk to all the exhibitions in both sections. Exhibitors will stamp your collection card for the prize draw. Chair: Prof. David Parker 13.30 – 13.55 INVITED LECTURE 8 Dynamic peptidic containers – expected and unexpected consequences of self-assembly Dr. Agnieszka Szumna (Polish Academy of Sciences, Warsaw) 13.55 – 14.20 INVITED LECTURE 9 Bright Luminescent Lanthanide Complexes as High Resolution Cellular Stains Dr. Robert Pal (Durham University) 14.20 – 14.45 INVITED LECTURE 10 Kinetically Robust Co(III) Assemblies Dr. Paul Lusby (University of Edinburgh) 15.00 – 15.30 COFFEE BREAK ES228/229 and ES230/231 There are posters and exhibitions in both spaces. Please take this opportunity to talk to all the sponsors in both sections. Exhibitors will stamp your collection card for the prize draw. All prize draw entries to be submitted. Chair: Prof. Mike Watkinson 15.30 – 15.55 MASC PhD AWARD LECTURE Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage Will Cullen (Sheffield University) 15.55 – 16.35 PLENARY LECTURE 4 Porous Organic Cages – A New Class of Porous Material Prof. Andrew I. Cooper (University of Liverpool) 16.35 – 17.15 PLENARY LECTURE 5 Sponsored by ChemComm and Chemical Science New Metal-Seamed Nanocapsules Based on Pyrogallol[4]arenes Prof. Jerry L. Atwood (University of Missouri – Columbia) 17.15 – 17.30 BEST POSTER & TALK AWARDS. THANKS & CLOSE
Abstracts
Bob Hay Lecture
MASC PhD Award
Plenary Lectures PL 1 – 5
Invited Lectures IL 1 – 10
Industrial Talks IND 1 – 2
Flash Talks F1 – 6
Posters
Bob Hay Lecture: Controlling Multicomponent Dipeptide Hydrogels E.R. Draper,a E.G.B. Eden,a T.O. McDonald,a C. Colquhoun,a K. Morris,b L. C. Serpellb and Dave J. Adamsa a Department of Chemistry, University of Liverpool, Crown Street, Liverpool, UK
b School of Life Sciences, Chichester II Building, University of Sussex,Falmer BN1 9QG, UK
Abstract: Low molecular weight gelators (LMWG) are molecules that self-assemble into one-dimensional fibrous structures. Under the right conditions, this self-assembly leads to the immobilisation of the solvent and the formation of a gel. These materials are attracting significant interest, for example in tissue engineering and cell culturing, where the low LMWG concentration needed can be useful, as can the gel’s reversibility as the cells grow and re-form their environment. In the majority of cases, gels are formed from a single LMWG. Mixing different LMWG (which all form gels independently) can be used to make interesting new materials.1-3 Depending on how these LMWG assemble, this could be used as a method to adjust the properties of the final gels, or to prepare systems with higher information content, for example by the selective positioning of specific functional groups in space. It is not only necessary to simply mix two LMWG, but to be able to finely control the assembly of both such that, ideally, their location in space is finely controlled. Here, we will describe a range of mixed dipeptide-based LMWG systems. We will show how fibrous structures form in these systems and show how we can control how different types of fibrous networks are built up in multicomponent systems. We describe both self-sorted and co-assembled networks (Fig. 1) and the effect of these different networks on the gel properties. Fig. 1 Schematic of possible assembly of two LMWG into fibres. (a) Self-sorting; (b) random co-assembly; (c) specific co-assembly. References 1. C. Colquhoun, E.R. Draper, E.G.B. Eden, B.N. Cattoz, K.L. Morris, L. Chen, T.O. McDonald, A.E. Terry, P.C.
Griffiths, L.C. Serpell and D.J. Adams, Nanoscale, 2014,6, 13719-13725 2. K.L. Morris, L. Chen, J. Raeburn, O.R. Sellick, P. Cotanda, A. Paul, P.C. Griffiths, S.M. King, R.K. O’Reilly, L.C
Serpell and D.J. Adams, Nature Commun., 2013, 4,1480 3. E.R. Draper, E.G.B. Eden, T.O. McDonald and D.J. Adams, Nature Chem., 2015, 7, 848-852.
PhD Award Lecture: Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage W. Cullen, M. C. Misuraca, C. A. Hunter, N. H. Williams, M. D. Ward The University of Sheffield, Dainton Building, Brook Hill, Sheffield, S3 7HF [email protected]
Abstract: The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic
reactions of small-molecule guests.1,2 One of the biggest challenges with artificial capsules as catalysts is
product inhibition. Often the favourable interactions that stabilise the transition state also stabilise the
product, and so the product often binds to the cavity too, thus inhibiting the reaction and preventing
catalytic turnover. This is a big limitation with the efficiency of such catalytic systems: they can be fast but
have few cycles.1,2
The M8L12 cubic cage binds neutral hydrophobic molecules, but not charged molecules. Using this, we
report a catalytic system that generates a charged product which does not bind in the cage cavity, thus
allowing catalytic turnover to occur. The reaction of interest is the Kemp elimination – reaction of
benzisoxazole with hydroxide to form 2-cyanophenolate. We found that, the rate enhancement is amongst
the largest so far observed: at pD 8.3, kcat/kuncat is 2 x 105, due to the accumulation of a high concentration
of partially desolvated hydroxide ions around the bound guest arising from ion-pairing with the 16+ cage.
Secondly, the catalysis is based on two orthogonal interactions: (i) hydrophobic binding of benzisoxazole in
the cavity, and (ii) polar binding of hydroxide ions to sites on the cage surface, both of which were
established by competition experiments. Hundreds of turnovers occur with no loss of activity due to
expulsion of the hydrophilic, anionic product.
1. C. J. Brown; F. D. Toste; R. G. Bergman; K. N. Raymond, Chem. Rev., 2015, 115, 3012-3035. 2. M. Yoshizawa; J. K. Klosterman; M. Fujita, Angew. Chem. Int. Ed., 2009, 48, 3418-3438
B
PL 1: Halogen-Bonded Soft Matter P. Metrangolo, G. Cavallo, T. Pilati, G. Resnati, G. Terraneo NFMLab, Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131, Milano, Italy [email protected]
According to the IUPAC, a halogen bond (XB) occurs when there is evidence of a net attractive interaction
between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic
region in another, or the same, molecular entity.1 Similarities between halogen and hydrogen bonds have
been emphasized in several contexts. However, it is the differences between these interactions that
provide with an extra value for the design and construction of XB-based supramolecular materials.2
Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates
using non-covalent interactions. There is significant interest in controlling the properties of such materials
by the formation of multicomponent systems, which exhibit non-additive properties emerging from
interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic
solvents is well established.
In this presentation I will highlight the use of halogen bonding to trigger supramolecular gel formation
in different systems such as peptide-based hydrogels3 and two-component gels (‘co-gel’).4 Other examples
of halogen-bonded soft materials will be presented, such as liquid crystals5 and supramolecular polymers.6
Nanofibrillation of the halogenated pentapeptides. AFM image close-up insets of (a) peptide DF(I)NKF(I), (b) peptide DF(I)NKF, and (c) peptide DF(Br)NKF(Br) (scale bar, 1 mm). (d–f) Height profiles of fibrils from a, b and c (cross-section lines highlighted in white). (g) Cross-sectional analysis on the top of a fibril segment in a showing a helicoidal profile along the longitudinal direction of the fibrils (highlighted in black). (h) Cryo-TEM images of the dried hydrogel of DF(I)NKF (scale bar, 200 nm). (i) In situ electron tomography of half-pitch helicoidal peptide DF(I)NKF(I).
1 G. R. Desiraju, P. S. Ho, L. Kloo, A. C. Legon, R. Marquardt, P. Metrangolo, P. Politzer, G. Resnati and K. Rissanen, Pure Appl. Chem., 2013, 85, 1711-. 2 A. Priimagi, G. Cavallo, P. Metrangolo and G. Resnati, Acc. Chem. Res., 2013, 46, 11, 2686-. 3 A. Bertolani, L. Pirrie, L. Stefan, N. Houbenov, J. S. Haataja, L. Catalano, G. Terraneo, G. Giancane, L. Valli, R. Milani, O. Ikkala, G. Resnati and P. Metrangolo, Nat. Commun., 2015, 6:7574, DOI: 10.1038/ncomms8574. 4 L. Meazza, J. A. Foster, K. Fucke, P. Metrangolo, G. Resnati and J. W. Steed, Nat. Chem., 2013, 5, 42-47. 5 D. W. Bruce, P. Metrangolo, F. Meyer, T. Pilati, C. Präsang, G. Resnati, G. Terraneo, S. G. Wainwright and A. C. Whitwood, Chem. Eur. J., 2010, 16, 9511-9524. 6 N. Houbenov, R. Milani, M. Poutanen, J. Haataja, V. Dichiarante, J. Sainio, J. Ruokolainen, G. Resnati, P. Metrangolo and O. Ikkala, Nat. Comm., 2015, 5:4043 | DOI: 10.1038/ncomms5043.
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PL 2: Molecular tectonics:
from molecules to crystal welding
Mir Wais Hosseini
Laboratoire de Tectonique Moléculaire, UMR UDS-CNRS 7140, University of Strasbourg, Institut Le Bel, 4, rue Blaise
Pascal, 67000 Strasbourg, France ([email protected])
The design and construction of periodic architectures in the crystalline phase are attracting
considerable interest over the last two de cades. For both design and analysis of molecular crystals,
we have developed a strategy called molecular tectonics which is based on the formation of
molecular networks through the design of complementary tectons or molecular construction units.
The generation of molecular networks and subsequently of crystals is achieved by self-assembly
processes based on repetitive molecular recognition events. This approach, combining
supramolecular synthesis and self-assembly processes in the solid state, is operational and versatile
and allows the design and construct a variety of complex purely organic or hybrid architectures.
Furthermore, molecular tectonics allows the design core-shell crystals and crystal welding. The
approach will be presented and illustrated by a variety of tectons and networks, core-shell crystals
and welded crystals.
1. M. W. Hosseini, Acc. Chem. Res., 38, 313 (2005).
2. M. W. Hosseini, Chem. Commun., Focus Article, ,582 (2005).
3. M. W. Hosseini, Cryts.Eng.Comm., 6, 318 (2004).
4. G. Marinescu, S. Ferlay, N. Kyritsakas, M. W. Hosseini, Chem. Commun., 2013, 49, 11209. 5. M. El Garah, N. Marets, S. Bonacchi, M. Mauro, A. Ciesielski, V. Bulach, M. W. Hosseini, P. Samori, J. Amer.
Chem. Soc. 2015, 137, 8450. 6. C. Adolf, S. Ferlay M. W. Hosseini, J. Amer. Chem. Soc. 2015, DOI: 10.1021/jacs.5b10586
PL 3: Development of supramolecular self-assembly architectures and materials
Thorri Gunnlaugsson
School of Chemistry and Trinity Biomedical Sciences (TBSI), Trinity College Dublin, The University of Dublin, Dublin 2, Ireland.
Self-assembly processes can give rise to the formation of novel supramolecular architectures and materials with unique function and properties. In supramolecular chemistry, the application of self-assembly processes and supramolecular polyme rization is being increasingly used to engineer and generate highly ordered and new structures (e.g. nano-structures and materials), with function or physical properties different to those of the starting material. However, it has often been difficult to elucidate and control the mechanism and to observe the formation of such structures in real-time. In this lecture the various examples of self-assembly structures and materials that our group in Dublin have developed over the last few years will be reviewed [1-5], which includes the formation of anion directed self-assembly capsules and clusters, d-metal ion based self-assembly cross-linked gels, lanthanide luminescent gels with healable properties, pyridine-urea gels possessing antibacterial properties, and supramolecular gels that provide platforms for nanowire growth., etc..
1 “Lanthanide luminescent logic gate mimics in soft matter: [H+] and [F-] dual-input device in a polymer gel with
potential for selective component release”, Samuel J. Bradberry, Joseph P. Byrne, Colin P. McCoy and Thorfinnur Gunnlaugsson, Chem. Commun. 2015, 51, 16565-16568. DOI: 10.1039/c5cc05009j
2 “Self-assembly formation of a healable lanthanide luminescent supramolecular metallogel from 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands”, Eoin P. McCarney, Joseph P. Byrne, Brendan Twamley, Miguel Martínez-Calvo, Gavin Ryan, Matthias E. Möbius and Thorfinnur Gunnlaugsson, Chem. Commun. 2015, 51, 14123-14126. DOI: 10.1039/C5CC03139G
3 “Crosslinking the fibers of supramolecular gels formed from a tripodal terpyridine derived ligand with d-block metal ions”, Oxana Kotova, Ronan Daly, Cidália M.G. dos Santos, Paul E. Kruger, John J. Boland and Thorfinnur Gunnlaugsson, Inorg. Chem. 2015, 54, 7735−7741. DOI: 10.1021/acs.inorgchem.5b00626
4 “Unexpected self-sorting self-assembly formation of a [4:4] sulfate:ligand cage from a preorganized ‘tripodal’ urea ligand”, Komala Pandurangan, Jonathan A. Kitchen, Salvador Blasco, Elaine M. Boyle, Bella Fitzpatrick, Martin Feeney, Paul E. Kruger and Thorfinnur Gunnlaugsson, Angew. Chem. Int. Ed. 2015, 54, 4566 –4570: DOI: 10.1002/anie.201411857R1 and 10.1002/ange.201411857R1
5 “Healable luminescent self-assembly supramolecular metallogels possessing lanthanide (Eu/Tb) depended rheological and morphological properties’ Miguel Martínez-Calvo, Oxana Kotova, Matthias E. Möbius, Alan P. Bell, Thomas McCabe, John J. Boland, Thorfinnur Gunnlaugsson, J. Am. Chem. Soc., 2015, 137, 1983–1992 DOI: 10.1021/ja511799n
a)# b)# c)#
d)#
Figure 3. a) Representation of the complex [(SO42-
)4.H44] showing the encapsulation of the four
sulfate anions (spacefill) inside the capsule formed by four molecules of H4 (stick representation,
different color per unit of H4). b) Spacefill representation of the complex [(SO42-
)4.H44] when viewed
down the c* crystallographic axis showing the arrangement and packing of the 44 self-assembly. c)
and d) Details of the Hydrogen bond network within the cavity.
PL 4: Porous Organic Cages – A New Class of Porous Material Andrew I. Cooper University of Liverpool, Department of Chemistry, Crown Street, Liverpool L69 7ZD, UK
In this lecture, I will outline our research in the area of porous organic cages. I will describe the unique
features of these materials, which are the first solution-processable crystalline porous organic solids.
Recently, this has led to new, counterintuitive materials, such as the first liquids with permanent
microporosity. I will also discuss the broader challenges in this research area, such as how we can predict
the crystal structures of organic materials from knowledge of their molecular building blocks alone. This
latter question is relevant to a wide range of functional organic solids.
Biography
Andy Cooper is the founding Academic Director of the Materials Innovation Factory at the University of
Liverpool. His research interests are polymeric materials, conjugated materials, porous organic crystals,
crystal engineering, supercritical fluids, materials for energy production, and high-throughput materials
methodology.
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PL 5: New Metal-Seamed Nanocapsules Based on
Pyrogallol[4]arenes
Jerry L. Atwood, Joshua White, Asanka Rathnayake, Philip H. Atwood, and Stuart G. Atwood
Department of Chemistry
University of Missouri-Columbia
Columbia, MO 65211
Since 2005, our group has published many articles on hexameric nanocapsules seamed by 24 metal
2+ ions. The only other hexameric nanocapsule stoichiometry has been 12 for those seamed by Ga3+
ions.
We have now discovered a synthetic route to hexameric nanocapsules based on C-alkylpyrogallol[4]arenes
seamed by 32 metal ions. In this initial discovery, the 32 metal ions comprise 16 Fe2+
and 16 Fe3+
ions. A
view of the skeleton of this new, mixed valence iron ion-seamed nanocapsule, [Fe32(C-
hexylpyrogallol[4]arene)6], shows that the sphere has no disorder. The self-assembly process brings
together 38 entities and the sites for the 2+ and 3+ ions are clearly defined.
The synthesis of the iron ion seamed nanocapsule was accomplished by the reaction of C-
hexylpyrogallol[4]arene with four equivalents of FeCl3 in a DMF/methanol solution in the presence of three
equivalents of sodium methoxide. The dark blue X-ray diffraction quality crystals were obtained over a
period of about one month. It should be noted that this is the first hexameric nanocapsule seamed by iron
ions. Previous attempts to prepare a hexameric nanocapsule seamed by 24 Fe2+
ions analogous to those of
Co2+
, Ni2+
, Cu2+
or Zn2+
have failed.
A range of new mixed valence metal ion seamed nanocapsules have now been synthesized.
IL 1: Structural flexibility in the solid state
L. J. Barbour University of Stellenbosch, Department of Chemistry, Stellenbosch, South Africa [email protected]
Abstract: In order to understand solid-gas inclusion processes at the molecular level it is
important to correlate physico-chemical data (e.g. sorption isotherms and calorimetric analysis) with
structural data. It is therefore desirable to carry out structural elucidation and calorimetric analysis under
conditions that closely mimic those of the sorption/desorption experiments. However, the crystallographic
analysis of samples under controlled gas environments poses significant technical challenges, particularly
given the limited space associated with the sample compartment of standard commercial diffractometer. In
this regard, an environmental gas cell has been developed in parallel with a pressure-programmed
differential scanning calorimeter. Use of these complementary techniques has provided new insight into
features such as pressure-induced phase transformations that give rise to inflections and hysteresis in
sorption isotherms. The influence of guest molecules on aspects such as structural flexibility and changes in
network interpenetration will be discussed.1-4
1 H. Aggarwal, R. K. Das, P. M. Bhatt and L. J. Barbour, Chem. Sci., 2015, 6, 4986. 2 C. X. Bezuidenhout, V. J. Smith, P. M. Bhatt, C. Esterhuysen and L. J. Barbour, Angew. Chem. Int. Ed., 2015, 54,
2079. 3 H. Aggarwal, P. Lama and L. J. Barbour, Chem. Commun., 2014, 50, 14543. 4 H. Aggarwal, P. M. Bhatt, C. X. Bezuidenhout and L. J. Barbour, J. Am. Chem. Soc., 2014, 136, 3776.
IL 2: Supramolecular routes to DNA-based Nanomaterials A. Houlton Chemical Nanoscience Lab, School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, [email protected]
Abstract: DNA is now an increasingly used component for synthetic chemists in the preparation of new materials.[1] Its size, topology, assorted chemical functional groups, allied with its capacity for self-assembly provides an extraordinary powerful nanoscale toolbox with which to design materials and nanoscale architectures.[2,3] However for numerous potential applications the lack of desirable opto-electronic properties of the native biopolymer is a considerable drawback.[4] Incorporating such functionality can be achieved by introducing pre-synthesised components, such as metal and inorganic nanoparticles and carbon nanotubes, into DNA-based structures.[1,5] An alternative route we are exploring is through supramolecular templating.[6-10] This approach exploits the non-covalent interactions between duplex DNA and synthetic polymer strands, such as polypyrrole, to form electrically supramolecular, DNA-templated, polymer nanowires. The generality of the method, details of the mechanism of formation of these conducting nanomaterials,[11] and possibilities for future developments will be discussed.
Figure. Left, AFM image of early stage DNA-templated supramolecular nanowire formation and, right, a snapshot of the MD simulation.
References 1. R. J. Macfarlane, M. R. Jones, B. Lee, E. Auyeung and C. A. Mirkin, Science, 2013, 341, 1222. 2. E. Braun and K. Keren, Adv. Phys., 2004, 53, 441-496. 3. N. C. Seeman, Ann. Rev. Biochem., 2010, 79, 65-87. 4. A. Houlton and S. M. D. Watson, Annu. Rep. Prog. Chem. A, 2011, 107, 21-42. 5. K. Keren, R. S. Berman, E. Buchstab, U. Sivan and E. Braun, Science, 2003, 302, 1380-1382. 6. L. Dong, T. Hollis, S. Fishwick, B. A. Connolly, N. G. Wright, B. R. Horrocks and A. Houlton, Chemistry Eur. J., 2007, 13, 822-828. 7. J. Hannant, J. H. Hedley, J. Pate, A. Walli, S. A. Farha Al-Said, M. A. Galindo, B. A. Connolly, B. R. Horrocks, A. Houlton and A. R. Pike, Chem. Commun., 2010, 46, 5870-5872. 8. R. Hassanien, M. Al-Hinai, S. A. Farha Al-Said, R. Little, L. Siller, N. G. Wright, A. Houlton and B. R. Horrocks, ACS Nano, 2010, 4, 2149-2159. 9. S. Pruneanu, S. A. F. Al-Said, L. Dong, T. A. Hollis, M. A. Galindo, N. G. Wright, A. Houlton and B. R. Horrocks, Adv. Funct. Mater., 2008, 18, 1-12. 10. S. M. D. Watson, J. H. Hedley, M. A. Galindo, S. A. F. Al-Said, N. G. Wright, B. A. Connolly, B. R. Horrocks and A. Houlton, Chemistry- Eur J. 2012, 18, 12008-12019. 11. S. M. D. Watson, M. A. Galindo, B. R. Horrocks and A. Houlton, J. Am. Chem. Soc., 2014, 136, 6649−6655; Editors' Choice Science, 558, 344. 2014.
IL 3: Molecular cages in solution...
or in nanomaterials?
Valeria Amendola Department of Chemistry, University of Pavia, via Taramelli 12, I-27100, Pavia, Italy [email protected]
Abstract: Molecular cages, bistren cryptands and cryptates in particular, are well-known versatile receptors
for anion inclusion in water.1 Macro-bicycles can be easily synthesised through the Schiff base condensation
of tren with the chosen dialdehyde, followed by the hydrogenation of the six imine bonds. The ellipsoidal
cavity of the cage can be varied at will, by choosing the appropriate dialdehyde, in order to include
substrates of varying sizes and shapes. Our group recently demonstrated that, by opportunely mixing
different spacers linking the tren units, new cages can be obtained with improved capabilities, e.g. in terms
of selectivity, to be applied as effective anion receptors2 and sensors.3 Asymmetric cryptates have been also
successfully immobilised on silica particles, gold nanostars and glass surfaces, opening new perspectives in
the development of materials with applications spanning from selective extraction of anionic pollutants4 to
biofilm eradication in medical devices.5
1 G. Alibrandi, V. Amendola, G. Bergamaschi, L. Fabbrizzi, M. Licchelli, Org. Biomol. Chem., 2015, 13, 3510 – 3524. 2 V. Amendola, G. Bergamaschi, M. Boiocchi, A. Poggi, M. L. Perrone, I. Viviani, Dalton Trans., 2014, 43(29), 11352-11360 3 V. Amendola, G. Bergamaschi, M. Boiocchi, R. Alberto, H. Braband, Chem. Sci., 2014, 5, 1820-1826 4 R. Alberto, G. Bergamaschi, H. Braband, T. Fox, V. Amendola, Angew. Chem. Int. Ed., 2012, 51, 9772 –9776; G. Alberti, V. Amendola, G. Bergamaschi, R. Colleoni, C. Milanese, R.Biesuz, Dalton Trans. 2013, 42, 6229-6234 5 V. Amendola, G. Bergamaschi, E. Cabrini, G. Da Carro, P. Pallavicini, N. Rossi, A. Taglietti, submitted
lease include a
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IL 4: Upper-rim Functionalisation of Calixarenes Including Inherently Chiral Racemic ABCD Calix[4]arenes S. P. Bew, G. R. Stephenson, D. H. Roy, W.H. Gardiner, M. B. Pitak, L. A. Martinez Lozarno, and S. J. Coles School of Chemistry, UEA, Norwich Research Park, Norwich, NR4 7TJ, UK [email protected]
Abstract: This talk will focus on our recent work towards developing upper-rim functionalised calixarenes
and the efficient application of an experimentally straightforward mechanochemical synthesis of upper-rim
functionalised prochiral ABBC calix[4]arenes. Exploiting their ease of formation subsequent transition-metal
mediated transformations provide the first straightforward route to structure and function diverse (i.e.
nitro, ester, alcohol, iodo, methoxy) racemic in herently chiral ABCD cone-confined calix[4]arenes.
IL 5: Calixarenes: From cluster formation to directed assembly S. J. Dalgarno Institute of Chemical Sciences, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS [email protected]
Abstract: Methylene-bridged calixarenes display markedly different coordination chemistry to their thia-,
sulfonyl- and sulfinyl-bridged analogues, and have recently emerged as excellent ligand supports for the
synthesis of polynuclear transition, lanthanide metal and 3d-4f clusters. The presentation will cover the
formation of a series of cluster motifs including MnIII2MnII
2(Calix[4])2 (Fig. 1),1 structurally related
MnIII2MnIILnIII(Calix[4])2 and MnIII
2LnIII2(Calix[4])2 (Fig. 1),2 MnIII
4LnIII4(Calix[4])4,
3,4 tri-capped trigonal prismatic
enneanuclear CuII9(Calix[4])3 and octahedral LnIII
6(Calix[4])2 (Fig. 1).5,6 Metal ion binding rules arising from
experiments with calix[4]arene will be discussed as they allow one to anticipate metal ion incorporation
upon extension to analogous chemistry performed with bis-calix[4]arene.7 Finally, alteration of the bis-
calix[4]arene linker will also be presented as a route to use cluster formation in the directed assembly of
new supramolecular architectures. 8
Figure 1. Series of structurally related calix[4]arene-supported Mn , Mn / Ln and Ln clusters formed under various conditions.
1 G. Karotsis, S. J. Teat, W. Wernsdorfer, S. Piligkos, S. J. Dalgarno, E. K. Brechin, Angew. Chem. Int. Ed., 2009,
48, 8285. 2 M. A. Palacios, R. McLellan, S. M. Taylor, C. M. Beavers, S. J. Teat, W. Wernsdorfer, S. Piligkos, S. J. Dalgarno, E.
K. Brechin, Chem. Eur. J., 2015, 21, 11212. 3 G. Karotsis, M. Evangelisti, S. J. Dalgarno, E. K. Brechin, Angew. Chem. Int. Ed., 2009, 48, 9928. 4 G. Karotsis, S. Kennedy, S. J. Teat, C. M. Beavers, D. A. Fowler, J. J. Morales, M. Evangelisti, S. J. Dalgarno, E. K.
Brechin, J. Am. Chem. Soc., 2010, 132, 12983. 5 G. Karotsis, S. Kennedy, C. M. Beavers, S. J. Teat, M. Evangelisti, E. K. Brechin, S. J. Dalgarno, Chem. Commun.,
2010, 46, 3884. 6 S. Sanz, R. D. McIntosh, C. M. Beavers, S. J. Teat, M. Evangelisti, E. K. Brechin, S. J. Dalgarno, Chem. Commun.,
2012, 48, 1449. 7 R. McLellan, M. A. Palacios, C. M. Beavers, S. J. Teat, S. Piligkos, E. K. Brechin, S. J. Dalgarno, Chem. Eur. J.,
2015, 7, 2804. 8 M. Coletta, R. McLellan, P. Murphy, B. T. Leube, S. Sanz, R. Clowes, K. J. Gagnon, S. J. Teat, A. I. Cooper, M. J.
Paterson, E. K. Brechin, S. J. Dalgarno, submitted.
IL 6: Sensing a Bacillis Anthracis Biomarker with well-known OLED Emitter EuTta3Phen M. A. Shipman, B. A. Blight* University of Kent, School of Physical Sciences, Canterbury UK, CT2 7NH, [email protected]
Abstract: Luminescent lanthanide (Ln) complexes have evolved into an important class of emitter with
applications in organic light-emitting diodes (OLEDs),1 sensors,2 and cellular imaging3 due to their distinct
and narrow f-f-emission bands, long lifetimes and broad stokes shifts.4 Of particular interest, is the
detection of 2,6-pyridine-dicarboxylic acid or dipicolinic acid (DPA). DPA is a unique bio-marker for bacterial
spore detection, as bacterial endospores can be comprised of up to 12% by weight DPA;5 Bacillus Antrhacis
is the endospore used in the delivery of the anthrax bioweapon.6 In this presentation, the use of a well
known Eu(III)-complex (common in OLED materials) as a potential DPA sensor will be demonstrated.
Furthermore, studies on the impact of aqueous- and phosphate-containing environments will be
considered.
1 J. Wang, R. Wang, J. Yang, Z. Zheng, M. D. Carducci, T. Cayou, N. Peyghambarian and G. E. Jabbour, J. Am. Chem. Soc. 2001, 123, 11378.
2 C. M. G. dos Santos, A. J. Harte, S. J. Quinn and T. Gunnlaugsson, Coord. Chem. Rev., 2008, 252, 2512.
3 A. Thibon and V. C. Pierre, Anal. Bioanal. Chem. 2009, 394, 107. 4 H. C. Aspinall, Chemistry of the f-Block Elements, Gordon and Breach Science Publishers, Amsterdam,
2001. 5 W. G. Murrel, The Bacterial Spore, Academic Press, New York, 1969. 6 J. A. Jernigan, D. S. Stephens, D. A. Ashford, C. Omenaca, M. S. Topiel, M. Galbraith, M. Tapper, T. L.
Fisk, S. Zaki, T. Popovic, R. F. Meyer, C. P. Quinn, S. A. Harper, S. K. Fridkin, J. J. Sejvar and C. W. Shepard, Emerg. Infec. Dis. 2001, 7, 933.
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IL 7: Guest sequestration, packing, and folding within water-soluble nano-capsules B. C. Gibb
Department of Chemistry, Tulane University, New Orleans, USA, [email protected]
Abstract: With an eye on the long-term goals of understanding nano-scale reactors, supramolecular
containers that assemble via the hydrophobic effect offer a unique perspective on many of the important
questions surrounding reaction control. Questions we are seeking to address include: what are the rules
regarding guest sequestration from a mixture? Do they self-sorting or not? How do guests orientate
and/or fold within yocto-liter volumes? And how do these and other factors relate to reaction outcome?
We will discuss out latest results pertaining to these questions.
IL 8: Dynamic peptidic containers – expected and unexpected consequences of self-assembly M. Szymański, M. Wierzbicki, H. Jędrzejewska, M. Gilski, M. Sztylko, P. Cmoch, A. Shkurenko, M. Jaskolski and A. Szumna Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland. [email protected]
Abstract: Self-assembled peptidic structures are gaining a lot of attention as biocompatible synthetic
materials for regenerative medicine or for drug delivery. However, application of ‘de novo’ designed
peptides, especially for formation of porous materials, is limited by conformational lability, tendency to
non-specific aggregation and low availability of long synthetic peptides in the large scale. Here we present
the spontaneous formation of peptidic capsules using easily available short peptides, dynamic covalent
chemistry (DCC) and self-assembly. Dynamic approach, supported by formation of minimal -barrel motifs,
allows for errors’ corrections and enables amplification of selected capsules from among a number of
possible products.
Numerous aspects of chiral self-sorting and self-assembly will be discussed including: self-assembly
induced tautomeric changes, switching of inherent chirality and mechanochemical methods to overpass
energy barriers for covalent and non-covalent assembly/disassembly and for complexation using fullerenes
as surface-inactive probes.
1 H. Jędrzejewska, M. Wierzbicki, P. Cmoch, K. Rissanen and A. Szumna, Angew. Chem. Int. Ed., 2014, 53, 13760–13764. 2. M. Grajda, M. Wierzbicki, P. Cmoch and A. Szumna, J. Org. Chem., 2013, 78, 11597–11601. 3. H. Jędrzejewska, M. Kwit and A. Szumna, Chem. Commun., 2015, 51, 13799-1380. 4. M. Wierzbicki and A. Szumna, Chem. Commun., 2013, 49, 3860-3862. 5. A. Szumna, Chem. Soc. Rev., 2010, 39, 4274-4285.
IL 9: Bright Luminescent Lanthanide Complexes as High Resolution Cellular Stains Robert Pal, Stephen J. Butler, Matthieu Starck and David Parker
Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK e-mail: [email protected]
The optical probes and cellular stains commonly used in microscopy are usually fluorescent organic molecules or recombinant proteins which have been used in many areas of cellular biology leading to an enhanced understanding of cellular processes and molecular interactions. However, many of these dyes have inherent drawbacks, such as issues associated with their toxicity, photostability and selectivity. Over the past few years, emissive lanthanide complexes have been shown to be alternative robust and bright cellular stains. These probes not only stain selected cellular organelles in a wide variety of cell lines, but also possess long lifetimes allowing ‘autofluorescence free’ time-gated detection to be achieved without perturbation of cellular homeostasis. [1]
Recent years show the emergence of novel optical microscopy techniques to surpass the optical diffraction barrier and visualize the ‘living’ cell in higher resolution. Governed by Abbe’s law, the highest achievable spatial resolution is dictated by the wavelength of excitation light d ~ λ(exc.)/2. The invention of confocal microscopy paved the way to the development of new optical (hardware) and software based super-resolution methodologies, such as SIM or STED. Since these techniques are limited by their well-known experimental drawbacks, [2] it is possible to improve lateral resolution using UV light as illumination source (Kohler 1904) with bright non-disruptive molecular probes.
We have set out to break the diffraction barrier and develop a novel super-resolution technique called Phase Modulation Nanoscopy (PhMoNa). [3] This technique is based on a novel combined structured illumination technique. The instrumental development involves modification of an existing confocal laser scanning microscope (LSCM) system, integrating a custom EOM within that allows frequency matched spatiotemporally (sinusoidal phase) modulated laser cluster excitation to be achieved with subsequent detection of cellular substructures with an 8 fold reduced voxel size compared to standard LSCM. In essence PhMoNa operates by utilizing an in situ generated optical grid pattern projected by the raster scanned excitation beam that subsequently introduces high spatial frequency mixing of the sub-diffraction size excitation cluster with the observed finite objects spatial frequencies. This approach allows experimental resolution in both lateral and axial domains to be improved by at least a factor of 2. Using a custom built (phase I) Electro Optical Modulator (EOM) in conjunction with newly synthesized functionalised Lanthanide(III) complexes as organelle probes, remarkable sub-diffraction ‘true experimental’ resolution of ~60 nm (lateral) was achieved in live-cell LSCM experiments, rendering this technique free from any unnecessary time consuming post-image processing deconvolution algorithms. The advantageous properties of the Ln(III) based probes have been further exploited in Durham in recent years, allowing high resolution visualization of selected cellular organelles in long term live-cell experiments, whilst also reporting on the micro-chemical environment using 355 nm laser excitation. [4] Owing to their beneficial photophysical and cellular accumulation properties, UV exposure and subsequent photo-bleaching/damage were minimized. Thus, we seek to develop the technique further to allow its use by the broad imaging community, so saturation eliminated high spatial resolution 3D reconstructions can be created by simply incorporating a small and affordable modular attachment into any existing LSCM setup. References: 1. S.J. Butler. M. Delbianco, L. Lamarque. B.K. McMahon, E. Neil. R. Pal. D. Parker, and J.M. Zwier, Dalton
Trans., 2015, 44, 4791 2. L. Schermelleh, R. Heintzmann and H. Leonhardt, J.Cell. Biol., 2010, 190, 165 3. R. Pal, Faraday Discuss., 2015, 177, 507 4. M. Starck, R. Pal and D. Parker, Chem. Eur. J., 2015 (accepted)
IL 10: Kinetically Robust Co(III) Assemblies Dr. Paul J. Lusby EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, Scotland EH9 3FJ., [email protected]
Abstract: Self-assembly procedures that utilise weak, reversible interactions have permitted access to a
wide and diverse set of discrete architectures, which have been further investigated for functional
properties such as catalysis1 or storage of reactive species2. Whilst these protocols provides obvious
synthetic benefits, such as quantitative yields and high atom efficiency, the dynamic nature of the
ensembles it produces can sometimes present certain problems. In the context of coordination assemblies,
one solution that has commonly been used to help improve structural integrity is the use of 2nd or 3rd row
transition metal ions. One problem with this approach, however, is similar to that encountered with
“standard” covalent synthesis; because the interactions are inherently less dynamic, often “mistakes”
cannot be rectified leading to much lower yields. Recently, we have developed an alternative method for
assembling non-equilibrium architectures that exploits the significant difference in substitutional lability of
CoII and CoIII.3 This “assembly-followed-by-locking” protocol possess both the benefits of conventional self-
assembly whilst producing systems with covalent-like levels of kinetic robustness. This talk will provide
further insight into the method, whilst comparing the use of a range of bis(bidentate) N,N-chelate donor
ligands for accessing different architectures. The host-guest properties and stimuli-responsive behaviour
will also be presented.
1 M. Yoshizawa, M. Tamura and M. Fujita, Science 2006, 312, 251-254. 2 P. Mal, B. Breiner, K. Rissanen and J.R. Nitschke, Science, 2009, 324, 1697-1699. 3 P. R. Symmers, M. J. Burke, D. P. August, P. I. T. Thomson, G. S. Nichol, M. R. Warren, C. J. Campbell and
P. J. Lusby, Chem. Sci. 2015, 6, 756-760.
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IND1: Advances in X-ray Crystallography M.J. Winter Rigaku Oxford Diffraction UnitB6, Chaucer Business Park, Watery Lane, Kemsing, Sevenoaks, TN15 6QY U.K. [email protected]
Abstract
Rigaku Oxford Diffraction formally commenced operations on the 29th April, 2015.
With the formation of the new organisation, the widest range of X-ray sources and X-ray area detectors are
available. The clear objective is to build upon all existing technologies and the expertise of the earlier
Rigaku and Oxford Diffraction entities to achieve optimal solutions covering all applications of
crystallography: in chemical, biological, physical, mineralogical, and materials science structural
applications.
The range of instrument configurations will be summarised, and illustrated with a number of particular
example applications.
IND 2: Highlighting innovative solutions for the integration of parallel evaporation with other Chemistry tools in the laboratory Ian Bailey Biopharma Process Systems Ltd Biopharma House Winnal Valley Rd Winchester SO23 0LD [email protected]
Abstract: This industrial flash talk highlights perhaps some of the lesser known solutions developed by
Genevac in recent years to integrate parallel evaporation with various other Chemistry tools in the
laboratory. Solutions include the innovative SampleGenie range and other formats to help streamline
processes which require an evaporation step for example, preparative HPLC fraction collection, compound
synthesis and scale up, thereby reducing manual handling of samples, improving compound recovery and
saving valuable time.
F1: Good, Better, Best! Limiting Superfluous
Ionophore Functionality Maximizes Effectiveness of a
Potentio-static Sensor for Creatinine.
L. Adriaenssens; D. Hernandez; P. Ballester; P. Blondeau
University of Lincoln, Joseph Banks Laboratories, Green Lane, Lincoln, LN6 7DL
Abstract: Potentiostatic sensors are ubiquitous in hospitals and labs the world over.1 They are easy for the
non-specialist to use and can be made cheaply and suitably robust for field work.2 Ionophores play a key
role in the effectiveness of potentiostatic sensors. Strong and specific host-guest interactions between the
ionophore and the analyte of interest give the sensors selectivity. Unfortunately, Ionophores are very
challenging to design for analytes like creatinine that diverge from simple geometries. Here, the
investigation of supramolecular interactions between creatinine and ionophores based on phophonate-
bridged calix[4]pyrroles is presented. Specifically, the relationship between the bridging substituents and
the selectivity of the resulting potentiostatic sensor reveal the importance of a obtaining a good match in
functionality between the ionophore and analyte while minimizing superfluous functionality.
1 P. Bühlmann, E. Pretsch and E. Bakker, Chem. Rev., 1998, 98, 1593–1688
2 M. Novell, T. Guinovart, P. Blondeau, F. X. Rius and F. J. Andrade, Lab chip, 2014, 14, 1308–1314
F2: Homo- and Hetero-Circuit [3]Rotaxane Formation in the Bipyridine-Mediated AT-CuAAC Reaction Edward. A. Neal,a Dr Stephen M. Goldupb aSchool of Biological and Chemical Sciences, Queen Mary University of London, E1 4NS
bSchool of Chemistry, University of Southampton, SO17 1BJ
Abstract: Rotaxanes are mechanically bonded compounds where macrocyclic components are permanently
threaded onto a dumbbell-like axle. Recent work in the Goldup Group has demonstrated that the yield of
[3]rotaxane formed is strongly dependent on macrocycle size when bipyridine macrocycles are employed in
Leigh’s1 “Active Template” Cu-mediated alkyne-azide cycloaddition reaction (AT-CuAAC).2
When larger macrocycles are employed in the bipyridine-mediated AT-CuAAC reaction, an unexpected
[3]rotaxane by-product is also formed from two macrocycles penetrated by a single axle, accounting for the
variation in [2]rotaxane yield with macrocycle size. Optimised syntheses of [2]- or [3]rotaxanes were
developed with good to excellent yields.3
By elucidation of the key parameters that favour [3]rotaxane formation a detailed mechanism of
[3]rotaxane formation was proposed.3 Building on this mechanistic proposal, experiments with two
different macrocycles in the same reaction afford sequence-selective or even sequence-specific
heterocircuit [3]rotaxanes.
1. V. Aucagne, J. Berná, J. D. Crowley, S. M. Goldup, K. D. Hänni, D. A. Leigh, P. J. Lusby, V. E. Ronaldson, A. M. Z. Slawin, A. Viterisi and D. B. Walker, J. Am. Chem. Soc., 2007, 129, 11950-11963.
2. H. Lahlali, K. Jobe, M. Watkinson and S. M. Goldup, Angew. Chem. Int. Ed., 2011, 50, 4151-4155.
3. E. A. Neal and S. M. Goldup, Chem. Sci., 2015, 6, 2398-2404.
F3: Imposing control on self-assembly: rational design and synthesis of a mixed-metal, mixed-ligand coordination cage containing four types of component Alexander J. Metherell and Michael D. Ward University of Sheffield, Sheffield, UK [email protected]
The syntheses of different types of metal/ligand polyhedral coordination cage provide examples of purely
serendipitous reactions, in which the structure of the product was entirely unexpected, to rationally-
designed reactions in which geometric rigidity of ligands and pronounced stereochemical preferences of
metal ions can be exploited. Most syntheses of cage complexes lie somewhere in between these extremes.
Retrosynthetic analysis of a previously reported1 [M16L24]32+ coordination cage shows how it can be
assembled rationally, in a stepwise manner, using a combination of kinetically inert and kinetically labile
components. Combination of the components of fac-[Ru(Lph)3](PF6)2, Cd(BF4)2 and Lnaph in the necessary 4 :
12 : 12 stoichiometry afforded crystals of [Ru4Cd12(Lph)12(L
naph)12]X32 (X = a mono-anion) in which the location
of the two types of metal ion [Ru(II) or Cd(II)] at specific vertices in the metal-ion array, and the two types
of bridging ligand (Lph and Lnaph) along specific edges, is completely controlled by the synthetic strategy.2
The incorporation of four different types of component at pre-determined positions in a coordination cage
superstructure represents a substantial advance in imposing control on the self-assembly of complex
metallosupramolecular entities.
1 M. D. Ward et al., J. Am. Chem. Soc., 2011, 133, 858. 2 A. J. Metherell and M. D. Ward, Chem. Sci., Advance Article, DOI: 10.1039/c5sc03526k.
F4: Detection of potassium ions with crown-ether appended lanthanide complexes A. K. R. Junker, M. Tropiano, S. Faulkner and T. J. Sørensen Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø, Denmark [email protected]
Abstract: Lanthanide centred luminesces can be used as a probe for changes in the molecular structure
occurring at a significant distance from the lanthanide in e.g. supramolecular structures.1,2 By exploiting
kinetically stable lanthanide complexes, made with cyclen-derived ligands, we have been able to design a
molecule combining reporting through lanthanide luminescence with the selective binding of alkali ions by
crown-ethers.3 The change in molecular structure as a result of the binding of the cation in the crown-ether
cavity is communicated to the lanthanide centre and can therefore be investigated by following the red or
green emission from the bound Eu(III) and Tb(III) ions.4,5 The lanthanide appended crown-ether complexes
were prepared by the CuAAC click reaction between an azide appended crown-ether and lanthanide
complexes of propargyl-DO3A.6 The resulting complexes are luminescent and exhibit an affinity for
potassium ions, which upon binding increases the observed luminescence of the complex without changing
the fine structure of the 5D0 to 4F0-7 emission bands of europium, indicating that the binding occurs without
changing the geometry at the lanthanide centre. The systems will be contrasted to see if more structural
information can be gleaned from their behaviour with and without cationic guests.
1 M. Tropiano, O. A. Blackburn, J. A. Tilney, L. R. Hill, T. J. Sørensen and S. Faulkner, J. Lumin., 2015, 167,
296-304. 2 M. Tropiano, O. A. Blackburn, J. A. Tilney, L. R. Hill, M. P. Placidi, R. J. Aarons, D. Sykes, M. W. Jones, A. M.
Kenwright, J. S. Snaith, T. J. Sørensen and S. Faulkner, Chem. Eur. J., 2013, 19, 16566-16571. 3 F. Arnaud-Neu, R. Delgado, S. Chaves, Pure Appl. Chem., 2003, 75, 71-102. 4 A. Thibon and V. C. Pierre, J. Am. Chem. Soc., 2009, 131, 434.435. 5 J. P. Leonard and T. Gunnlaugsson, J. Fluoresc., 2005, 15, 585-595. 6 C. Allain, P. D. Beer, S. Faulkner, M. W. Jones, A. M. Kenwright, N. L. Kilah, R. C. Knighton, T. J. Sørensen
and M. Tropiano, Chem. Sci., 2013, 4, 489-493.
N
N
NN
N
O
O
O
O
ON
N
O
O
O
OO
O
O
LnK+
N
NN
N
O
O O
Ln
O
O ON3
O
O
OO
O
O
"Cu(II)"
N
N
NN
N
O
O
O
O
ON
N
O
O
O
OO
O
O
Ln
KCl
F5: Self-assembly path of amyloidogenic peptides
incorporating halogen-bond donor groups
L. Lascialfari,a A. Bertolani,a A. Pizzi,a A. Gori,a N. Demitri,b G. Resnati,a P. Metrangoloa a) NFMLab, Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131 Milano, Italy; b) Elettra Synchrotron, Trieste, Italy. [email protected]
Abstract: Amyloid fibrils, formed by the tight assembly of β-sheet-like structures, are widely studied
because of their disease-related implications and because the robustness of their supramolecular
architectures can be exploited in nanostructured bio-inspired materials.1 It is at the same time true that,
the halogenation of proteins is a consequence of oxidative-stress, which is often associated to misfolding
and aggregation.2 Intrigued by these two aspects, we tried to see if it was possible to find a correlation,
hopefully synergistic, between the hydrogen bond interactions commonly used by amyloidogenic systems
to self-assemble and the halogen bond, which is, instead, sparingly present in biological systems.
Some of us have already reported on the effect of the presence of halogens in specific sites of the
amyloidogenic sequences DFNKFa (Fig. 1), demonstrating that halogenation, and in particular iodination,
strongly promoted its fibril formation ability and affected the structure of formed fibrils.3
In order to demonstrate that this positive effect on the self-assembly abilities is truly related to the fact
that the iodine atoms are involved in intermolecular interactions that cooperate with the conventional
intermolecular interactions, we synthesised, through a new synthetic procedure, the aminoacid 1 (Fig. 1,
left). In 1, the iodine atom, as demonstrated by X-Ray analysis of 1-N-methylacetamide co-crystals,4 is more
prone to act as halogen bond donor, if compared with the corresponding not fluorinated analogue used in
ref. [3]. Preliminary self-assembly studies show that the DFNKFb peptide has a fast gelation kinetic and a
higher thermal stability if compared with the most efficient peptide of the DFNKFa series. The DFNKFb is
still under investigation in our laboratories, but the obtained results corroborate the thesis that the halogen
bond may play a significant role in triggering self-assembly in biomimetic systems.
Figure 1. Left: chemical structure of the modified aminoacid; right: studied amyloidogenic peptides
1 S. Mankar, A. Anoop, S. Sen, S. K. Maji, Nano Rev. 2011, 2, 6032-6043. 2 J. R. Mazzulli, R. Hodara, S. Lind, H. Ischiropoulos, Prot. Rev. 2006, 4, 123-133 (2006). 3 A. Bertolani, L. Pirrie, L. Stefan, N. Houbenov, J. S. Haataja, L. Catalano, G. Terraneo, G. Giancane, L. Valli, R.
Milani, O. Ikkala, G. Resnati and Pierangelo Metrangolo, Nature Commun. 2015, 6, 7574. 4 V. Vasylyeva, S. K. Nayak, G. Terraneo, G. Cavallo, P. Metrangolo and G. Resnati, CrystEngComm, 2014, 16,
8102-8105.
F6: Nanoscale SAMul heparin binders as promising
clinical tools Ana C. Rodrigo, Stephen M. Bromfield, David K. Smith Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. [email protected]
Abstract: Our work develops self-assembling nanoscale systems able to interact with biological polyanions.
Heparin, an anionic polysaccharide, is a vital biomolecule in clinical use as anticoagulant during major
surgery, which requires neutralisation once surgery is complete in order for clotting to begin.1 Currently the
only licenced heparin antidote is protamine sulfate, although not without allergic and other adverse
responses in a significant number of patients. Furthermore, given the ubiquitous, and relatively poorly
understood natural biological roles of heparin, we aim to develop highly tuneable and degradable self-
assembling multivalent (SAMul) nanosystems as protamine alternatives, and to study how heparin can
effectively bound and intervene in heparin-mediated processes.2
We present here our latest SAMul nanostructures, which demonstrate – using data from our novel Mallard
Blue heparin binding assay3- that the morphology of the self-assembled nanoscale structure can profoundly
affect binding behaviour. Additionally, synthetically-straightforward modifications to the monomer units
can influence the overall binding preferences of the resulting SAMul assemblies. Excitingly, the facile
tuneability offered by this approach gives great potential to provide chemical tools able to probe or
intervene in biological systems, whilst also demonstrating the acute sensitivity of biological polyanions to
the molecular structure of the binding unit.
We hope that by beginning to understand biological polyanion binding using this SAMul approach, a
clinically relevant alternative to protamine will emerge.
1 S. M. Bromfield, E. Wilde and D. K. Smith, Chem. Soc. Rev., 2013, 42, 9184-9195 2 (a) A. Barnard and D. K. Smith, Angew. Chem. Int., Ed. 2012, 51, 6572– 6581 (b) S. M. Bromfield, P. Posocco, C. W. Chan, M. Calderon, S. E. Guimond, J. E. Turnbull, S. Pricl and D. K. Smith, Chem. Sci., 2014, 5, 1484-1492. 3 (a) S. M. Bromfield, A. Barnard, P. Posocco, M. Fermeglia, S. Pricl and D. K. Smith, J. Am. Chem. Soc., 2013, 135, 2911-2914 (b) S. M. Bromfield, P. Posocco, M. Fermeglia, S. Pricl, J. Rodríguez-López and D. K. Smith, Chem. Commun., 2013, 49, 4830-4832.
Heparin
P1: A glycosidase enzyme mimic based on a bipodal histidine conjugate Mousumi Samanta and Subhajit Bandyopadhyay Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur, Nadia, WB 741246, India [email protected]
Abstract: Nature has evolved the glycosidase enzymes that efficiently cleave the highly stable glycosidic
bonds present in oligo/polysaccharides. The naturally occurring glycosidases use the highly conserved Asp-
Glu or Glu-Glu dyads in their active sites.1 It was recently observed that the Asp-His catalytic dyad can also
act as a glycosidase via general acid-base mechanism.2 The use of histidine in the enzyme active site of
glycosidase has inspired us to construct a glycosidase enzyme mimic having His-His dyad.3 The mimic was
found to be highly efficient with a rate enhancement of five orders in magnitude compared to the non-
catalysed reaction at the optimum pH of 6.8 where the concentration of the catalytically active acid-
conjugate base form, having a protonated and a neutral imidazole, was also maximum (Figure 1). The
pHrate profile diagram shows that the mechanism proceeds through a general acid-base mechanism. The
kinetic parameters obtained with the enzyme mimic with four different model glycosidic substrates
demonstrated that the His-His dyad functions efficiently as a glycosidase mimic with a value of upto 3.29 ×
10-4 s-1 for the kcat with the 4-nitrophenyl-β-D-glucopyranoside, and 9.2 mM for the KM with 4-nitrophenyl-
β-D-galactopyranoside.
Figure 1: Singly protonated form of enzyme mimic
References: 1) (a) D. J. Vocadlo, G. J. Davies, R. Laine and S. G. Withers, Nature, 2001, 412 , 835-838; (b) G. Paes, J. G. Berrin and J.
Beaugrand, Biotech. Adv., 2012, 30, 564−592. 2) S. Litzinger, S. Fischer, P. Polzer, K. Diederichs, W. Welte and C. Mayer, J. Biol. Chem., 2010, 285, 35675–35684.
3) This recent reference discusses the role of the his residue in details: S. S. Macdonald, M. Blaukopf and S. G. Withers, J. Biol. Chem., 2015, 290, 4887-4895.
P2: Photoinduced phase transitions in halogen-bonded liquid crystals F. Fernandez-Palacio,1 M. Poutanen,2 M. Saccone,3 A. Siiskonen,2 G. Terraneo,1 G. Resnati,1 O. Ikkala,2 P. Metrangolo,1 and A. Priimagi3 1
NFMLab, DCMIC ”Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, I-20131 Milan, Italy. 2 Department of Applied Physics, Aalto University, P.O. Box 15100, FI-00076 Aalto, Finland.
3 Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, FI-33101 Tampere,
Finland. [email protected]
Fifteen new supramolecular liquid crystals (LCs) are presented in this work. The complexes have been
formed through halogen bonding between five promesogenic stilbazole molecules and three
photoresponsive halogen bonding1 donors synthetized for the first time within this research project (see
Figure). All the liquid crystals described in this work feature enantiotropic mesophases, except for the
complex with the longest alkyl chain, which exhibited a monotropic LC phase.
The cis-state of the studied azobenzenes is particularly interesting, due to the unusually long measured life-
time, equal to 13 days at 20°C. Photoresponsivity has been used to induce an isothermal nematic-to-
isotropic transition in the supramolecular liquid crystalline phase. In order to understand the orientation of
the molecules in the different phases, birefringence has been measured. The obtained results revealed high
values, conceivably related to the good orientation of the LC phase. Illumination of the sample (395 nm) led
to nematic-to-isotropic transition in about 3 seconds. Furthermore, an observed drop in the birefringence
value seemed to indicate the disappearance of the orientational order (i.e., a transition to an isotropic
phase). The transition has been attributed to the isomerization of the azo molecules from the rod-like form
of trans-isomers to the bent form of cis-isomers. The liquid crystalline phase reappeared within seconds
after switching off the irradiation, so a system presenting a completely reversible transition is presented. In
addition to these features, our systems undergo a phase transition from the crystalline to the liquid state
under irradiation with UV light within ca. 30s at temperature below the melting point. Within minutes, the
recrystallization occurs through a partial nematic LC phase, and result is a homogeneous crystalline phase.
Although a seminal work of Ikeda2 has been published for dye doped covalent LCs, the recently developed
supramolecular Low-Molecular Weight Liquid Crystalline Actuators (LMWLCA) have not been investigated
in depth, yet. The versatility of the supramolecular approach to LMWLCAs may provide the possibility to
overcome common problems encountered with dye doped LCs, i.e., phase separation of the dye. Our
approach using halogen bonding has been demonstrated particularly reliable and robust. Our future efforts
will extend research in this direction.
The complexes prepared in this study are assembled by halogen bonding between promesogenic stilbazole molecules (left) and photoresponsive
halogen bonding donors (right).
1. A. Priimagi, G. Cavallo, P. Metrangolo and G. Resnati, Acc. Chem. Res., 2013, 46, 2686-2695 2. J.-H Sung, S. Hirano, O. Tsutsumi, A., Kanazawa, T. Shiono and T. Ikeda, Chem Mater.,2002, 14, 385-391
P3: Zinc(II) Coordination Networks based on an Azobenzene-containing Halogen Bond-Donor Ligand F. Fernandez-Palacio,1 M. Saccone,2 L. Catalano,1 T. Pilati,1 G. Terraneo,1 G. Resnati,1 P. Metrangolo1
1
NFMLab, DCMIC ”Giulio Natta”, Politecnico di Milano, Via Mancinelli 7, I-20131 Milan, Italy. 2 Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, FI-33101 Tampere,
Finland. [email protected]
The goal of this work is to develop Metal Organic Frameworks (MOFs) combining a photoresponsive group
and halogen bond-donor sites and to study their functional properties. Therefore, two new azobenzene
molecules 1 and 2 (Fig. 1) have been synthesized. These dyes were decorated by dimethylamino group in
one ring and two carboxylic groups in the other to extend the dimensinality of our coordination system
and, in fact, they allowed us to obtain new coordination networks with Zn(II). Three iodine atoms are
present in 1, while they are absent in 2 in order to see the effect of the inclusion of halogen bond-donor
sites on the network structure and properties. As far as we know, these are the first coordination networks
involving both azobenzene molecules and halogen bonding.1
We obtained our structures in different conditions, by hydrothermal synthesis or isothermal evaporation,
and by using different organic molecules as additional linkers (bipyridine, dipyridylethylene, and also
pyridine). Single crystal X-ray diffraction studies revealed that iodine atoms function as good halogen bond-
donor sites coordinating the solvent included in the framework.2 Our preliminary photochemical studies
confirm the formation of the cis isomer of the ligand in solution. Such outcomes are important in view of
the design and synthesis of halogen-bonded azobenzene-containing photoresponsive MOF.
Figure 1: Synthesized azobenzene ligands with iodines (1) and without (2).
1. F. Fernandez-Palacio, M. Saccone, L. Catalano, G. Terraneo, T. Pilati, P. Metrangolo, G. Resnati. Manuscript in preparation. 2. R. Bertani, P. Sgarbossa, A. Venzo, F. Lelj, M. Amati, G. Resnati, T. Pilati, P. Metrangolo and G. Terraneo, Coord. Chem. Rev., 2010, 254, 677-706
P4: Healable Luminescent Self-Assembly Supramolecular Lanthanide (Eu/Tb) Metallogels M. Martínez-Calvo,a O. Kotova,a M. E. Möbius,b J. J. Bolandc and T. Gunnlaugssona* a School of Chemistry, Trinity Biomedical Sciences Institute (TBSI) and Trinity College Dublin, Dublin 2, Ireland
b School of Physics, Sami Nasr Institute of Advanced Materials (SNIAM) and Trinity College Dublin, Dublin 2, Ireland
c School of Chemistry, Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN) and Trinity College
Dublin, Dublin 2, Ireland [email protected]
Abstract: Herein we present the use of lanthanide directed self-assembly formation (Ln(III) = Eu(III), Tb(III))
in the generation of luminescent supramolecular polymers, that when swelled with methanol give rise to
self-healing supramolecular gels. These were analysed by using luminescent and 1H NMR titrations studies,
allowing for the identification of the various species involved in the subsequent Ln(III)-gel formation. These
highly luminescent gels could be mixed to give a variety of luminescent colours depending on their
Eu(III):Tb(III) stoichiometric ratios. Imaging and rheological studies showed that these gels prepared using
only Eu(III) or only Tb(III) have different morphological and rheological properties, that are also different to
those determined upon forming gels by mixing of Eu(III) and Tb(III) gels (Figure 1). Hence, our results
demonstrate for the first time the crucial role the lanthanide ions play in the supramolecular
polymerization process, which is in principle a host-guest interaction, and consequently in the self-healing
properties of the corresponding gels, which are dictated by the same host-guest interactions.1
Figure 1. Left: Chromaticity diagram (CIE) for Tb(III), Eu(III) and Eu(III)/Tb(III) gels; Right: healing experiment showing gels in the day light, under UV light, gel after being cut in half and self-healing properties of the gel.
1 M. Martínez-Calvo, O. Kotova, M. E. Möbius, A. P. Bell, T. McCabe, J. J. Boland and T. Gunnlaugsson, J. Am. Chem. Soc., 2015, 137, 1983-1992.
P5: The Rapid Synthesis and Dynamic Behaviour of an Isophthalamide [2]Catenane 1 Calum N. Marrs and Nicholas H. Evans Department of Chemistry, Lancaster University, Lancaster. LA1 4YB. UK. [email protected]
Abstract: Catenanes and rotaxanes are no longer simply curiosities of synthetic chemistry, but are
increasingly being used in nanotechnological applications,2 many of which exploit the relative motion of
their interlocked components.3 As a part of our research programme, we are looking to exploit the 3D
topologies of catenanes and rotaxanes to generate effective hosts for ionic and molecular guests.4
Interlocked molecules may be prepared by the use of various template methodologies (e.g. cations, anions,
- stacking, hydrogen bonding, halogen bonding, etc.) that overcome the entropically unfavourable
association of multiple molecular components that is required for their preparation.5 While a large number
of synthetic strategies have been reported to date, many involve lengthy multi-step procedures to obtain
the precursors required for the final reaction step that leads to covalent capture of the interlocked
molecule. This represents a considerable hurdle for the useful application of catenanes and rotaxanes.
Here we report a serendipitously discovered [2]catenane that was prepared via a short synthetic route. By
reacting a bis-amine (prepared in two steps) with commercially available isophthaloyl chloride, an
isophthalamide [2]catenane was produced – in just three reaction steps. In addition to NMR and MS
characterisation, the structure of the catenane has been unequivocally confirmed by solid state structural
determination (see Figure). 1H NMR studies reveal that the rings rotate relative to one another in solution,
in a process that may be controlled by varying solvent or temperature.
Figure: X-ray structure of isophthalamide [2]catenane.
1 C. N. Marrs and N. H. Evans, Org. Biomol. Chem., 2015, DOI: 10.1039/C5OB01770J. 2 S. F. M. van Dongen, S. Cantekin, J. A. A. W. Elemans, A. E. Rowan and R. J. M. Nolte, Chem. Soc. Rev., 2014,
43, 99-122. 3 S. Erbas-Cakmak, D. A. Leigh, C. T. McTernan and A. L. Nussbaumer, Chem. Rev., 2015, 115, 10081-10206. 4 M. J. Langton and P. D. Beer, Acc. Chem. Res., 2014, 47, 1935-1949. 5 (a) N. H. Evans and P. D. Beer, Chem. Soc. Rev., 2014, 43, 4658-4683; (b) M. Xue, Y. Yang, X. Chi, X. Yan and F.
Huang, Chem. Rev., 2015, 115, 7398-7501.
P6: Redox Driven Self-assembly of Polyoxometalates V. Duros, Z. Hosni, H. N. Miras, L. Cronin WestCHEM School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK, [email protected]; [email protected]
Abstract: Polyoxometalates (POMs) are a class of inorganic compounds that have
attracted the interest of chemists over the last two centuries because of a variety of disciplines and
applications such as chemical analysis, catalysis, medicine and electronics as well as their nanoscale
dimensions, ranging from 1 to 10 nm1. Up to now, two methods have been employed from our group in
order to investigate the self-assembly mechanisms governing the formation of POMs, standard one-pot and
flow approaches (linear and networked systems).1,2,3 Herein, we report the application of the fuzzy logic
concept in the aforementioned investigation. Fuzzy logic is a form of many-valued logic in which the truth
values of variables may be any real number between 0 and 1.4 By contrast, in Boolean logic, the truth
values of variables may only be 0 or 1.5 The reason for applying the fuzzy logic concept was to control the
degree of reduction of POM clusters and obtain a gradient between the reduced and the oxidised regions,
therefore intermediate electronic and structural states being concurrently present on solution, on a time
scale that would allow crystallization.1,2 As a proof of concept, we were able to obtain X-ray quality crystals
corresponding to the Mo154 cluster using as a driver of the fuzzy logic the redox potential linked to the
percentage of reduction in the Mo atoms.
Figure 1: (LEFT) Conceptual representation of the self-assembly mechanism for the formation of Mo blues, (RIGHT) A gradient of oxidised and reduced regions where interesting compounds can arise.
1 H. N. Miras and L. Cronin, J. Am. Chem. Soc., 2012, 134, 3816-3824. 2 H. N. Miras and L. Cronin, Science, 2010, 327, 72-74. 3 C. J. Richmond and L. Cronin, Nature Chem., 2012, 4, 1037-1043. 4 https://en.wikipedia.org/wiki/Fuzzy_logic as of October 2015. 5 V. Novák and J. Močkoř, Mathematical principles of fuzzy logic, 1999, Dodrecht: Kluwer Academic.
P7: Anion-Templated Self-Assembly of {Mo24Fe12} Macrocycles Featuring Supramolecular Tetrahedron Architecture
W. Xuan, A. J. Surman, Q. Zheng, D-.L. Long, L. Cronin* WestCHEM School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK, [email protected]; [email protected]
Abstract: Anion templated self-assembly has emerged as a highly effective synthetic approach to construct
a wide range of finite and infinite supramolecular architectures.1 As a class of metal−oxygen−anion clusters,
polyoxometalates (POMs) have recently been employed as ‘anionic templates’ due to their variable
charges, sizes and diverse geometries.2,3 Accordingly, some gigantic POMs clusters have been built via the
templation of smaller POMs such as Keggin-type anion {PMo12}, Dawson-type {P2W18}, and {Mo36}.4-6
We are particularly interested in developing POMs-templated self-assembly as general approach to
fabricate highly complex POMs, with the aim to understand the underlying principle of POMs-templated
host-guest system. To this end, a series of {Mo24Fe12} macrocycles featuring supramolecular tetrahedron
architecture is discovered via POMs-templated self-assembly. The anionic templates could be either
produced in-situ or added directly as external director. The formation mechanism is revealed for this host-
guest system and transformation between macrocycles is realized by template-exchange. More
importantly, the concept of using {Mo24Fe12} as confined reaction vessel is achieved by in-situ generation of
uncapped Dawson {P2Mo12} within macrocycle.
Figure 1. LEFT: Anion-templated self-assembly of a series of {Mo24Fe12} macrocycles; RIGHT: View of the
supramolecular tetrahedron built from four {Mo24Fe12} macrocycles and the resultant 3D network.
1 P. D. Beer and P. A. Gale, Angew. Chem. Int. Ed., 2001, 40, 486-516. 2 J. Lü, J.-X. Lin, M.-N. Cao and R. Cao, Coord. Chem. Rev., 2013, 257, 1334-1356. 3 D.-Y. Du, J.-S. Qin, S.-L. Li, Z.-M. Su and Y.-Q. Lan, Chem. Soc. Rev., 2014, 43, 4615-4632. 4 A. Müller, S. K. Das, P. Kögerler, H. Bögge, M. Schidtmann, A. X. Trautwein, V. Schünemann, E. Krickmeyer, W.
Preetz, Angew. Chem. Int. Ed., 2000, 39, 3414-3417. 5 X, Fang, L. Hansen, F. Haso, P. Yin, A. Pandey, L. Engelhardt, I. Slowing, T. Li, T. Liu, M. Luban and D. C.
Johnston, Angew. Chem. Int. Ed., 2013, 52, 10500-10504. 6 H. N. Miras, G. J. T. Cooper, D.-L. Long, H. Bögge, A. Müller, C. Streb and L. Cronin, Science., 2010, 327, 72-74.
P8: A Chemical Biology Approach to Understanding Self-Assembling Supramolecular Peptide Structures Samuel J. Bunce, Andy J. Wilson, Sheena E. Radford and Alison E. Ashcroft School of Chemistry, University of Leeds, LS2 9JT [email protected]
Abstract: Understanding the self-assembly of proteins/peptides into highly ordered supramolecular
structures is of key importance; both as a fundamental biological process and to elucidate the underlying
mechanisms of pathological disease states such as amyloidosis .1 Studying these highly complex systems,
that involve many energetically different assembly pathways and intermediary structures, requires the use
of a wide range of analytical and biophysical techniques. One of the most applicable is Photoinduced
Crosslinking (PIC) in which transient and/or weak supramolecular connectivity is transformed into a stable
covalent form, providing analytically tractable products under conditions that may ordinarily produce
disassembly.2,3 Therefore this technique is particularly well suited to explore amyloidogenic peptide
systems, such as fragments from the Alzheimer’s beta (Aβ) peptide, in which fleeting intermediary
structures may play a key role in the pathogenesis of degenerative diseases. This presentation will describe
the synthesis of a photoactivatable amino acid analogue (TFMD-Phe) and preliminary studies on Aβ16-22
fibril formation.
Figure 1. A cartoon representation illustrating how a PIC experiment is undertaken. A peptide containing photoactivatable TFMD-Phe undergoes self-assembly, then structures are irradiated forming a stable covalent link which can be analysed using ion-mobility-spectrometry – mass-spectrometry (IMS-MS).
References 1 F. Chiti and C. M. Dobson, Annu. Rev. Biochem., 2006, 75, 333–366. 2 G. W. Preston and A. J. Wilson, Chem. Soc. Rev., 2013, 42, 3289–301. 3 G. W. Preston, S. E. Radford, A. E. Ashcroft and A. J. Wilson, Anal. Chem., 2012, 84, 6790–6797.
P9: Chiral macrocyclic europium(III) complexes for security tagging and labelling A. T. Frawley,a S. J. Butler,b R. Pal,a D. Parker.a
a Department of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK.
b Department of Chemistry, Loughborough University, Loughborough, Leicestershire, LE11 3TU, UK
Email: [email protected]
Highly emissive sensitised lanthanide complexes based on macrocyclic chelating ligands have been used
extensively to study biological function at a cellular level, due to their long-lived, sharp emission bands and
high stability.1 These photophysical properties also make these complexes promising candidates for
security labelling and as anti-counterfeiting tools.
Counterfeiting is a global problem, affecting everybody from the individual consumer right up to
governments and multinational organisations. The annual cost of counterfeiting to the global economy is
estimated to be $1.7 trillion,2 and in the last 10 years, the Bank of England has withdrawn over 5 million
counterfeit banknotes from circulation with a total face value of nearly £100 million.3
Chiral europium complexes such as that shown in Fig. 1 may be resolved by chiral HPLC. Each enantiomer
gives rise to mirror-image circularly polarised luminescence (CPL). This unique fingerprint can be exploited
as an additional security feature for the labelling of authentic items such as banknotes, certificates and
clothes labels. Simple methods of detection of the complexes have been developed using band pass filters
attached to a commercially-available DSLR camera and flash lamp. Using this setup and introducing a time
delay between excitation and capture of an image, other emitted light can be filtered out, leaving only the
image produced by the labelling agent. Any counterfeit that does not possess the correct photophysical
properties will not appear in the image.
Figure 1. Structure of the RRR-Λ-(δδδ) enantiomer and CPL spectra of enantiomeric complexes.
1. S. J. Butler, M. Delbianco, L. Lamarque, B. K. McMahon, E. R. Neil, R. Pal, D. Parker, J. W. Walton and J. M. Zwier, Dalton Trans., 2014, 44, 4791-4803. 2. Roles and responsibilities of intermediaries: Fighting counterfeiting and piracy in the supply chain, International Chamber of Commerce, Paris, 2015. 3. The Bank of England, www.bankofengland.co.uk/banknotes/Pages/about/counterfeits.aspx, (accessed Nov 2015).
P10: Gelation Landscape Engineering using a Multi-Reaction Supramolecular Hydrogelator System G. O. Lloyd Heriot-Watt University, Riccarton, Edinburgh, Scotland, U.K. EH14 4AS [email protected]
Abstract: Both thermodynamic and kinetic
constraints can control self-assembly processes
to result in pathway selection in the assembly of
supramolecular materials. The resultant
assemblies or materials can have vastly different
properties, depending on the chosen self-
assembly path. Thermodynamically, pushing an
assembly down a particular pathway to a stable
energy well within the assembly landscape can
utilise solvent, temperature or pH changes.
Kinetically the landscape can be navigated using
the activation energies associated with certain
assembly processes, to address not only metastable states over time but also kinetically trap a certain
state. Materials generated from these complex pathways can include crystal forms (polymorphism),
viruses, protein networks, supramolecular polymers and certain low molecular weight gelators (LMWGs).1
We will present work on the simultaneous control of the kinetics and thermodynamics of two different
types of covalent chemistry which results in pathway selectivity in the formation of hydrogelating
molecules from a complex reaction network (Fig. 1).2 This can lead to a range of hydrogel materials with
vastly different properties, starting from a set of simple starting compounds and reaction conditions. These
are a chemical reaction between a water-soluble trialdehyde and the tuberculosis drug isoniazid resulting in
the formation of either one, two or three hydrazone connectivity products, meaning kinetic gelation
pathways can be addressed. The thermodynamics control the formation of either a keto or an enol
tautomer of the products, thus resulting in vastly different materials. Overall, this shows that careful
navigation of a reaction landscape using both kinetic and thermodynamic selectivity can be used to control
material selection from a complex reaction network. We will also present our latest results on the self-
assembly and self-sorting of mixed compounds utilising similar chemistry in hydrogelation.
References 1 a) P. A. Korevaar, S. J. George, A. J. Markvoort, M. M. J. Smulders, P. A. J. Hilbers, A. P. H. J. Schenning, T. F. A. De Greef & E. W. Meijer, Nature, 2012, 481, 492; b) P. A. Korevaar, C. J. Newcomb, E. W. Meijer & S. I. Stupp, J. Am. Chem. Soc., 2014, 136, 8540; c) J. Raeburn, A. Z. Cardoso & D. J. Adams, Chem. Soc. Rev., 2013, 42, 5143. 2 J. S. Foster, J. M. Żurek, N. M. S. Almeida, W. E. Hendriksen, V. A. A. le Sage, V. Lakshminarayanan, A. L. Thompson, R. Banerjee, R. Eelkema, H. Mulvana, M. J. Paterson, J. H. van Esch and G. O. Lloyd, J. Am. Chem. Soc., 2015, in press, DOI: 10.1021/jacs.5b06988.
Figure 1. The pathway complexity reaction network
diagram shows the supramolecular assembly of three
hydrogels from a single starting point (*) of dissolved
core and periphery components.
P11: Towards Dynamic Combinatorial Chemistry at Physiological pH. Patrick L Higgs, Antonio Ruiz-Sanchez, Benjamin R Horrocks, Andrew G Leach, David A Fulton* Chemical Nanoscience Laboratory, School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU [email protected]
Abstract: The application of Dynamic Combinatorial Chemistry (DCC) depends upon component exchange
processes to mediate structural reconfiguration and self-assembly.1 Acyl hydrazone bonds are popular in
DCC, however, a great limitation is that their optimal exchange rates are obtained at pH 4.5 which prevents
the application of this chemistry within the biological arena. Herein, we report hydrazone exchange at
physiological pH by preparing a selection of hydrazone substrates from aromatic carbonyl compounds
which possess structural moieties known to catalyse rapid hydrazone formation. Rate-enhancing proton
donor/acceptor moieties were embedded directly within the aromatic hydrazone component to assist the
rate-limiting step by mediating intramolecular proton transfer to collapse the aminal intermediate.2 The
component exchange kinetics of each hydrazone substrate were investigated by 1H NMR spectroscopy over
the pH range 5.4-7.4. The experimental rate constants and activation energies obtained by computational
modelling of transition states were largely consistent, and indicate that hydrazones derived from
quinolone-8-carbaldehyde mediate effective component exchange at physiological pH, with a 3-5 fold rate
enhancement compared to hydrazones derived from benzaldehyde. This finding constitutes our first step
towards in vitro DCC, where reversible chemistry permits an evolving interaction between library members
and nature’s own biomolecular architectures.3
References:
1 P. T. Corbett, J. Leclaire, L. Vial, K. R. West, J. L. Wietor, J. K. M. Sanders and S. Otto, Dynamic Combinatorial Chemistry. Chem. Rev., 2006, 106, 3652-3711.
2 E. T. Kool, D. H. Park and P. Crisalli, Fast hydrazone reactants: electronic and acid/base effects strongly influence rate at biological pH. J. Am. Chem. Soc., 2013, 135, 17663-17666.
3 C. S. Mahon and D. A. Fulton, Mimicking nature with synthetic macromolecules capable of recognition. Nature Chemistry, 2014, 6, 665-672.
Heteroatom proton donor/acceptor
P12: Cocrystals of Lactams and Boronic Acids Melissa J. Goodwina, Jonathan W. Steeda and Osama M. Musab [email protected] aDepartment of Chemistry, Durham University, South Road, Durham, DH1 3LE, UK
bAshland Speciality Ingredients, 1005 Route 202/206, Bridgewater, NJ 08807, USA
Abstract: Lactams, such as pyrrolidone and caprolactam, are a set of compounds with a very diverse range
of uses. Their polymers are often water soluble and biologically friendly, leading to many applications in
cosmetics,1 blood plasma replacement2 and gas hydrate inhibition3 to name but a few. The polar carbonyl
moiety of the lactam group imparts a large majority of the lactams’ properties, making studying the
interaction of the carbonyl an area of interest. Single crystal x-ray crystallography of cocrystals is one way
to glean insight into the interactions of the carbonyl moiety with different compounds.
Bishydroxypyrrolidone (bisHEP) and bisvinylcaprolactam (bisVP) are small molecule models of kinetic
hydrate inhibitor (KHI) polymers which are commercially used to prevent clathrate formation in oil and gas
pipelines. Study of their interactions with different species may offer insight into the mechanism of
clathrate inhibition. Boronic acids are a class of Lewis acids of the form R-B(OH)2 where R is a hydroxyl
group or any organic group. Their ability as hydrogen bond donors makes boronic acids ideal candidates to
cocrystallise with the hydrogen bond accepting lactams. Two new cocrystals of lactam containing
compounds with boronic acids have been prepared. Slow evaporation of a 1:1 mixture of bisVP and
tetrahydroxydiboron gave a 1:1 ε-caprolactam/boric acid cocrystal and slow evaporation of a 1:1 mixture of
bisHEP and benzenediboronic acid gave a 1:1 bisHEP/ benzenediboronic acid cocrystal.
1 A. L. Micchelli and F. T. Koehler, J. Soc. Cosmet. Chem., 1968, 19, 863–880.
2 H. J. McDonald and R. H. Spitzer, Circ. Res., 1953, 1, 396–404.
3 A. Perrin, O. M. Musa and J. W. Steed, Chem. Soc. Rev., 2013, 42, 1996–2015.
Single crystal x-ray structure of
bisHEP/benzene diboronic acid cocrystal
Single crystal x-ray structure of ε-
caprolactam/boric acid cocrystal
P13: Robust Metallo-Organic Assemblies M. J. Burke, G. S. Nichol, P. J. Lusby EaStCHEM School of Chemistry, University of Edinburgh, King’s Buildings, David Brewster Road, Edinburgh, EH9 3FJ. [email protected]
Abstract: Recently there has been significant interest in coordination-driven supramolecular cages and
capsules, particularly in relation to the functions or properties that they possess as a result of their well-
defined cavities.1-3
We recently described an assembly-followed-by-fixing method for producing “non-equilibrium” M4L6
tetrahedral assemblies that exploits the significant difference in substitutional lability of CoII and CoIII.4 We
now provide further insight and mechanistic detail whilst comparing the use of a range of bis(bidentate)
N,N-chelate donor ligands for accessing different architectures.
1 M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed., 2009, 48, 3418. 2 P. Mal, B. Breiner, K. Rissanen, J. R. Nitschke, Science, 2009, 324, 1697. 3 C. J. Brown, R. G. Bergman, K. N. Raymond, J. Am. Chem. Soc., 2009, 131, 17530. 4 P. R. Symmers, M. J. Burke, D. P. August, P. I. T. Thomson, G. S. Nichol, M. R. Warren, C. J. Campbell and P. J.
Lusby, Chem. Sci., 2015, 6, 756.
P14: Knotted Urea-Based Gels: Atomistic and Coarse-Grained Simulations of Urea-Tape Formation K. E. Horner, M. A. Miller, J. W. Steed Department of Mathematical Sciences, Durham University, South Road, Durham, DH1 3LE. [email protected]
Abstract: In 1867, Lord Kelvin suggested that all atoms were comprised of knotted tubes of the surrounding
aether.1 Whilst this later turned out not to be the case, it did start a long-running fascination with knots.
This interest has since spread through many subjects, beginning with knot theory in mathematics and later
extending to fields such as chemistry, physics and anthropology. Knots within all of these subjects are the
focus of the research of the Scientific Properties of Complex Knots (SPOCK) group based in Durham and
Bristol in the UK.
One thread of this research is the study of the formation of urea-based supramolecular gel networks. These
gels are formed by the self-assembly of urea gelators into urea tapes which then aggregate and arrange
into fibres and finally into an extended, tangled mesh.2 The factors which influence these structures are not
entirely clear, but the opportunity for knot formation within these networks is obvious.
Atomistic molecular dynamics simulations on varying numbers of small bis(urea) gelators were carried out
in vacuo as well as in simulated boxes of water or acetone. There was no aggregation of the gelators in
water simulations, which is expected from experimental results, but varying degrees of aggregation in
acetone and vacuum simulations. These atomistic simulations can be used to provide parameters for a
coarse-grained model based on spherocylinders, each with attractive patches mimicking the two urea
groups within each gelator. Every spherocylinder has "A" patches and two "B" patches corresponding to H-
acceptor and H-donor groups of the urea moieties. The "A" patches can only interact with "B" patches and
vice versa which allows the coarse-grained model to simulate the H-bonding which is key to urea-tape
formation. These H-bonding interactions have been studied in closer detail with ab initio magnetic shielding
calculations
The simulation parameters are fully tuneable, in particular, the spherocylinders themselves can be altered
to model a range of different gelators. This includes programming different cylinder lengths, distances
between patches, cylinder end sizes and even having flexible centre sections. We will also trial knocking out
the functionality of random attractive patches to model the effects of anion-tuning.2 It is hoped that these
simulations will provide valuable insight into the process of urea-tape formation and ultimately the
formation of the whole gel network. In this way, we can study the inclusion or exclusion of knotted
structures within gels and the effect this has on overall properties.
1 W. Thomson, Philos. Mag. Ser. 4, 1867, 34, 15-24. 2 J. W. Steed, Chem. Soc. Rev., 2010, 39, 3686-3699.
P15: Pyrene derivatives as heparin sensors in highly competitive aqueous solution and serum: Effect of self-assembled multivalency (SAMul) Ching W. Chan, David K. Smith* Department of Chemistry, University of York, Heslington, York, YO10 5DD [email protected]
Abstract: Clinically, heparin has been commonly used as an anticoagulant during cardiopulmonary surgery
and to treat emergency deep venous thrombosis (DVT).1 Quantifying heparin levels in blood is typically
achieved via activated clotting time assay, such as the aPTT technique or anti-Xa assay with the drawback of
relatively slow, and not being performed on the patient in a simple manner in situ.2 Therefore, it is of
interest to developing heparin sensors which operate under biologically relevant conditions and in highly
competitive media.3, 4 Multivalency is an effective and widely employed way of achieving high-affinity
interactions between nanoscale surfaces.5-7 The self-assembled multivalency (SAMul) approach to making
multivalent systems which only requires the synthesis of smaller “drug-like” monomer units that
spontaneously self-assemble into a nanoscale ligand array and are presented to the target for binding.8
Hereby we designed and synthesized SAMul pyrene derivatives Py-G1 and non-SAMul pyrene derivatives
Py-DAPMA in which the pyrene unit can act as a build-in sensor. We report the effects of heparin sensing
with and without a pre-assembled SAMul approach.
Py-G1 Py-DAPMA 1. J. Fareed, D. A. Hoppensteadt and R. L. Bick, Semin. Thromb. Hemost., 2000, 26, 5-22. 2. J. W. Vandiver and T. G. Vondracek, Pharmacotherapy, 2012, 32, 546-558. 3. S. M. Bromfield, A. Barnard, P. Posocco, M. Fermeglia, S. Pricl and D. K. Smith, J. Am. Chem. Soc.,
2013, 135, 2911-2914. 4. S. M. Bromfield, E. Wilde and D. K. Smith, Chem. Soc. Rev., 2013, 42, 9184-9195. 5. C. Fasting, C. A. Schalley, M. Weber, O. Seitz, S. Hecht, B. Koksch, J. Dernedde, C. Graf, E.-W. Knapp
and R. Haag, Angew. Chem. Int. Ed., 2012, 51, 10472-10498. 6. A. Mulder, J. Huskens and D. N. Reinhoudt, Org. Biomol. Chem., 2004, 2, 3409-3424. 7. M. Mammen, S. K. Choi and G. M. Whitesides, Angew. Chem. Int. Ed., 1998, 37, 2755-2794. 8. A. C. Rodrigo, A. Barnard, J. Cooper and D. K. Smith, Angew. Chem. Int. Ed., 2011, 50, 4675-4679.
P16: Preparation of a ‘4-Node’ pH-Redox Dual-Stimuli
Responsive Network
Michael E. Bracchi and David A. Fulton* Chemical Nanoscience Laboratory, School of Chemistry, Newcastle University, NE1 7RU. [email protected]
Abstract: Systems chemistry1 aims to investigate system level phenomenon in complex chemical systems
comprised of well characterized components, potentially shedding light on how complex chemical systems
operate in nature. A pH-redox dual stimuli-responsive system has been designed in which stimuli-
responsive polymers serve as supramolecular building blocks with the capacity to interconvert between a
variety of distinct nanoscale architectures. Firstly, A small molecule model system, analogous to the pH-
redox sensitive polymer system, was designed, synthesized and investigated to determine the extent of
orthogonality and reversibility of the disulfide and imine chemistries by 1H NMR spectroscopic analysis.2
This model system provided confidence to then develop a macromolecular system based on the same
orthogonal dynamic covalent bonding motifs. The polymeric building blocks, prepared by reversible
addition-fragmentation chain transfer (RAFT) polymerization, are designed to incorporate pendant sites for
imine (pH-sensitive) and disulfide (redox-sensitive) dynamic covalent cross-links. The system’s anticipated
stimuli-responsive behavior was mapped into a ‘4-node’ network, each node representing one of four
distinct, interconvertible architectures. Sequential application of two orthogonal stimuli drives nano-scale
structural reorganization in a way dictated by the order in which stimuli are applied. Changes in pH effects
the forming and breaking of imine cross-links whereas changes in redox environment drives the formation
and cleavage of disulfide cross-links. Such dynamic systems pertain towards types of ‘programmed’ self-
assembly behaviors observed in Nature.
1. R. F. Ludlow and S. Otto, Chem. Soc. Rev., 2008, 37, 101-108. 2. M. E. Bracchi and D. A. Fulton, Chem. Commun., 2015, 51, 11052-11055.
Please include a
300 dpi picture of
yourself here. Do
not alter the size
of the box
(2.5x2.5cm)
Disulfide cross-linked
nanoparticle.
Imine cross-linked
nanoparticle.
Imine & disulfide cross-linked
nanoparticle.
Unassociated random
terpolymers.
P17: Macrocyclic Metal Complex-DNA Conjugates for Electrochemical Base Discrimination J. –L. H. A. Duprey, J. Carr-Smith, S. L. Horswell, J. Kowalski and J. H. R. Tucker School of Chemistry, University of Birmingham, Birmingham, UK [email protected]
DNA is an ideal scaffold for the assembly of nanoscale architectures due to its well-understood
structure, high programmability and the ease in which derivatives can be synthesised containing
non-natural components. In particular, the incorporation of metal-containing moieties into DNA[1]
has become a highly attractive field of study due to the range of potential applications, which
include the development of DNA nanotechnology and electrochemical sensors. We will present
work detailing the successful incorporation of metal cyclidene moities[2] into DNA via automated
synthesis. This has resulted in a new family of readily prepared electrochemical probes that are
capable of distinguishing between single nucleobases in target DNA strands through different
changes in current intensity upon duplex formation.
1 H.V. Nguuyen, Z. Zhao, A. Sallustrau, S. L. Horswell, L. Male, A. Mulas and J. H. R. Tucker, Chem. Commun.., 2012, 48, 12165-12167.
2 I Mames, A. Rodger and J. Kowalski, Eur. J. Inorg. Chem. 2015, 4, 630-639.
P18: Dynamic Polymer Gels in the Oil and Gas Industries Jesús del Barrio,*,1 Dominique Hoogland,2 Isabelle Atheaux, 1 Oren A. Scherman,2 Seth Hartshorne1 1Schlumberger Gould Research, Madingley Road, Cambridge, UK CB3 0EL.
2Melville Laboratory
for Polymer Synthesis, Department of Chemistry, The University of Cambridge, Cambridge CB2 1EW. *E-mail: [email protected]
Abstract: The oil and gas industry currently makes use of viscoelastic polymer systems for a number of
applications such as reservoir stimulation and enhanced oil recovery. In hydraulic fracturing, in particular,
guar-based fracturing fluids are the preferred choice. These polymer fluids transmit the pressure, which is
applied at the surface, and also transport proppant, typically sand, into the fractures. Hydrated guar and
derivatives result in linear gels that do not achieve the required viscosity for proppant transport at elevated
temperatures. Therefore, crosslinkers including boron, zirconium or titanium species are used to increase
the viscosity of the fluid system. In general, borate-crosslinked fluids are preferred because of their
reversibility to mechanical shearing, their favourable environmental properties and their wide tolerance to
water-quality issues. However, borate-crosslinked fluids exhibit a relatively large temperature and pressure
sensitivity.1 Collaborative efforts between the Melville Laboratory for Polymer Synthesis (The University of
Cambridge) and the Gould Research Center (Schlumberger) are focused on developing novel chemistries to
dynamically crosslink polymers in water, which include host‒guest chemistry and polymer modification.
1 M. D. Parris, B. A. Mackay, J. W. Rathke, R. J. Klinger and R. E. Gerald II Macromolecules, 2008, 41, 8180-8186.
P19: Supramolecular interactions of the 2,6-bis(1,2,3-triazol-4-yl)pyridine [btp] motif – self-assembly and interlocked structures Joseph P. Byrne, Salvador Blasco, Miguel Martínez-Calvo, Thorfinnur Gunnlaugsson Trinity College Dublin, the University of Dublin, Dublin 2. [email protected]
Abstract: The btp motif is a versatile supramolecular binding site prepared conveniently via the CuAAC
‘click’ reaction; it possesses interesting coordination properties with transition metals ions, lanthanide ions
and indeed anions, as well as having applications in polymer formation and molecular logic.1 Here we show
the one-pot synthesis of chiral btp ligands from enantiopure amines with retention of sterochemistry and
that in addition to binding lanthanide(III) ions, the btp motif has the capacity to form dimeric species
through the weak supramolecular interactions of the triazolyl and pyridyl moieties, as evidenced by X-ray
diffraction.2 This intriguing behaviour may be used to build higher order systems.
Interlocked molecules are of great interest to the supramolecular community and ring-closing methathesis
(RCM) has been used as a strategy to ‘clip’ pre-organised threads together.3 Exploiting the btp⋅⋅⋅btp
interactions, mentioned above, has allowed the formation of self-templated supramolecular species which
gave rise to mechanically interlocked molecules without metal templation upon RCM, namely [2]catenanes.
The interlocked structure was confirmed by X-ray diffraction.4
1 (a) J. P. Byrne, J. A. Kitchen and T. Gunnlaugsson, Chem. Soc. Rev., 2014, 43, 5302-5325; (b) Y. Li, J. C. Huffman
and A. H. Flood, Chem. Commun., 2007, 2692-2694; (c) J. P. Byrne, J. A. Kitchen, O. Kotova, V. Leigh, A. P. Bell, J. J. Boland, M. Albrecht and T. Gunnlaugsson, Dalton Trans., 2013, 43, 196-209; (d) E. Brunet, O. Juanes, L. Jiménez and J. C. Rodríguez-Ubis, Tetrahedron Lett., 2009, 50, 5361-5363; (e) C. Zhang, X. Shen, R. Sakai, M. Gottschaldt, U. S. Schubert, et al., J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 746-753; (f) S. J. Bradberry, J. P. Byrne, C. P. McCoy and T. Gunnlaugsson, Chem. Commun., 2015, 51, 16565-16568.
2 J. P. Byrne, M. Martínez-Calvo, R. D. Peacock and T. Gunnlaugsson, Chem. Eur. J., 2015, In press, DOI: 10.1002/chem.201504257.
3 (a) S. M. Goldup, D. A. Leigh, P. J. Lusby, R. T. McBurney, A. M. Z. Slawin, Angew. Chem. Int. Ed., 2008, 47, 6999-7003; (b) D. A. Leigh, P. J. Lusby, R. T. McBurney, A. Morelli, A. M. Z. Slawin, A. R. Thomson, D. B. Walker, J. Am. Chem. Soc., 2009, 131, 3762-3771; (c) N. G. White, P. D. Beer, Chem. Commun., 2012, 48, 8499-8501; (d) C. Lincheneau, B. Jean-Denis, T. Gunnlaugsson, Chem. Commun., 2014, 50, 2857-2860.
4 J. P. Byrne, S. Blasco and T. Gunnlaugsson, manuscript under preparation.
P20: Pharmaceutical crystal modification using tailored gelators S. R. Kennedy and J. W. Steed Durham University, Department of Chemistry, Durham University, South Road, Durham, UK. [email protected]
Abstract: Tailored gelators are of particular interest as crystal growth media for pharmaceutical molecules
as a gel removes convection effects while introducing tailored nucleation sites. Using gels as crystal growth
media instead of solvent only crystallisation can effect crystal size or lead to habit modification while
potentially giving rise to new polymorphic forms.1,2
Bis(urea) gelators are of particular interest due to both the relative ease of synthesis and the fibre forming
nature of the bis(urea) leading to the formation of fibrous networks that can immobilise solvents. Typical
synthesis involves a simple one-pot reaction between an amine and an isocyanate. As a result amine
derived pharmaceutical molecules are of particular interest as they can be used for the direct synthesis of
gelators tailored towards that specific drug molecule.
Gelators tailored towards isoniazid crystal growth have been synthesised and gelation experiments have
been carried out in various solvents. Crystallisation experiments were subsequently carried out on isoniazid
both in solvent and in the tailored gels to establish differences in crystallisation behaviour.
1. J. A. Foster, M.-O. M. Pipenbrock, G. O. Lloyd, N. Clarke, J. A. K. Howard and J. W. Steed, Nature Chem., 2010, 2, 1037. 2. K. Fucke, N. Qureshi, D. S. Yufit, J. A. K. Howard and J. W. Steed, Cryst. Growth Des., 2010, 10, 880.
P21: Naphthalimide-derived diaryl ethers as luminescent linkers for metallosupramolecular architectures Chris S. Hawes,a Amy D. Lynes,a Thorfinnur Gunnlaugssona aSchool of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, Dublin 2,
Ireland [email protected]
Abstract: Naphthalimides and related compounds are well known to display distinctive and appealing
luminescent properties, particularly when substituted with electron donor groups.1 The large π-systems in
such compounds are also potent structure-directing agents capable of influencing extended structure
through well-defined π-π interactions.2 The reaction of 4-nitro-1,8-naphthalimides bearing pendant
coordinating groups with a range of substituted phenols gives a library of divergent, luminescent ligands in
good yields. Reaction of these species with transition metal ions generates coordination polymers of
varying dimensionalities, where the extended structures are dominated by the interactions of the ligand π-
systems. As well as forming coordination polymers on reaction with d-block metal ions, ligand HL1 readily
forms hydrogels when deprotonated in the presence of alkali metal cations. The structural, spectroscopic
and host-guest properties of the resulting materials have been explored and rationalised in the context of
the underlying interactions.
1 S. Banerjee, J. A. Kitchen, S. A. Bright, J. E. O’Brien, D. C. Williams, J. M. Kelly and T. Gunnlaugsson, Chem.
Commun. 2013, 49, 8522-8524; S. Banerjee, E. B. Veale, C. M. Phelan, S. A. Murphy, G. M. Tocci, L. J. Gillespie, D. O. Frimannsson, J. M. Kelly and T. Gunnlaugsson, Chem. Soc. Rev. 2013, 42, 1601-1618; R. M. Duke, E. B. Veale, F. M. Pfeffer, P. E. Kruger and T. Gunnlaugsson, Chem. Soc. Rev. 2010, 39, 3936-3953
2 S. Burattini, B. W. Greenland, D. H. Merino, W. Went, J. Seppala, H. M. Colquhoun, W. Hayes, M. E. Mackay, I. W. Hamley and S. J. Rowan, J. Am. Chem. Soc. 2010, 132, 12051-12058; S. A. Boer, C. S. Hawes and D. R. Turner, Chem. Commun. 2014, 50, 1125-1127.
P22: Enhanced Guest Binding in Organic Solvents D. P. August, P. J. Lusby EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, Scotland EH9 3FJ. [email protected]
Abstract: Metallosupramolecular capsules have received considerable interest in recent years due to their
applications in areas such as catalysis,1 drug delivery2 and sensing.3 Many of these areas rely on guest
binding, either to increase the reactivity for catalysis4 or to stabilise the compound for storage.5 In the
context of metallosupramolecular capsules, the hydrophobic effect has been the most widely exploited
method used to encapsulate apolar guests. Whilst this works well for cage-systems that are completely
soluble in water, solvophobicity drops off rapidly in mixed aqueous systems. Another approach to binding
uses specific capsule-guest interactions such as hydrogen bonding; in contrast, the strength of these is
often maximised in less polar, organic solvents. Here we describe the guest binding properties of Pd2L4 type
capsules in such solvents, further showing how the affinities can be fine-tuned across several orders of
magnitude by simply altering the associated counter anions.
1 M. D. Pluth, R. G. Bergman and K. N. Raymond, Science, 2007, 316, 85–88. 2 W. Cullen, S. Turega, C. A. Hunter and M. D. Ward, Chem. Sci., 2015, 6, 625–631. 3 H. Ahmad, B. W. Hazel, A. J. H. M. Meijer, J. A. Thomas and K. A. Wilkinson, Chem. – A Eur. J., 2013, 19, 5081–
5087. 4 M. Yoshizawa, M. Tamura and M. Fujita, Science, 2006, 312, 251–254. 5 P. Mal, B. Breiner, K. Rissanen and J. R. Nitschke, Science, 2009, 324, 1697–1699.
P23: Gelation studies of silver(I) metallogel of imidazole containing urea derivative Maya A. M. Arif & Jonathan W. Steed Department of Chemistry, Durham University South Road, Durham DH1 3LE United Kingdom [email protected]
Abstract:
A series of imidazole ligands containing urea derivatives have been prepared conveniently from histamine.
We are interested in using these compounds to produce metal-switched supramolecular gels. Of all the
ligands synthesised, only ligand 3 (Figure 1) formed metallogels in THF:water (7:3) mixtures in the presence
of up to 2.0 equivalent of silver metal with weakly coordinating anions such as silver(I) tetrafluoroborate
(Figure 2), silver(I) perchlorate and silver(I) hexafluorophosphate. In contrast, upon addition of AgNO3,
precipitates formed immediately instead of a gel. It is suggested that the dodecyl chains of ligand 3
facilitate the formation of the fibrous networks due to the strong Van der Waals interactions between them
and solvophobic effects.1 Nevertheless, due to the poor solubility of the ligand-silver aggregates the gels
are not thermoreversible.2,3
Figure 1 Series of imidazole ligands containing urea derivatives
Figure 2 SEM micrograph of the xerogel with 0.5 equivalent of AgBF4 at 1% (w/v)
The strength of the gel is also exemplified by the high yield stress, in which the metallogel reaches a
pronounced maximum yield stress at 0.5 equivalent of AgBF4, suggesting a 2 : 1 ratio to be optimum for
gelation, consistent with the 2-coordinate nature of Ag(I) and the monodentate nature of ligand 3.2,3
However, addition of more than 0.5 equivalent of AgBF4 (up to 2 equivalents) significantly reduces the
strength of the metallogel. It is possible that excess silver ions form silver nanoparticles on exposure to light
which that may affect the rheological behavior of the metallogel.
(1) Dawn, A.; Andrew, K. S.; Yufit, D. S.; Hong, Y.; Reddy, J. P.; Jones, C. D.; Aguilar, J. a.; Steed, J. W. Cryst. Growth Des. 2015, 15, 4591–4599.
(2) Piepenbrock, M.-O. M.; Clarke, N.; Steed, J. W. Soft Matter 2011, 7, 2412–2418. (3) Lee, J. H. Y. H. Y.; Kang, S.; Lee, J. H. Y. H. Y.; Jung, J. H. Soft Matter 2012, 8, 6557–6563.
P24: Differentially Addressable Cavities within Metal–Organic Cage-Cross-Linked Polymeric Hydrogels
J. A. Foster, R. M. Parker, A. M. Belenguer, N. Kishi, S. Sutton, C. Abell, J. R. Nitschke University of Sheffield, Department of Chemistry, Sheffield, S3 7HF [email protected]
Abstract: We present1-2 a new class of hydrogels formed by polymers that are cross-linked through
subcomponent self-assembled metal–organic cages. Selective encapsulation of guest molecules within the
cages creates two distinct internal phases within the hydrogel, which allows for contrasting release profiles
of related molecules depending on their aptitude for encapsulation within the cages. The hydrogels were
fabricated into microparticles via a droplet-based microfluidic approach and proved responsive to a variety
of stimuli, including acid and competing amine or aldehyde subcomponents, allowing for the triggered
release of cargo.
Water soluble polymers functionalised with cage subcomponents cross-link upon cage formation to create hydrogels that are capable of selectively binding guest molecules within the cage cavities.
Other hydro- and organo-gels incorporating different metal−organic or organic cage moieties with internal
cavities capable of binding guests, such as drug molecules, fragrances or pesticides, may be accessible using
the methods here presented. The host−guest properties of cages have also been exploited in a variety of
other ways, for example, as homogeneous catalysts and sensors and incorporating cages into the gel phase
opens up the possibility of undertaking these same processes heterogeneously, allowing for the separation
of products and recovery of the cages. Metal−organic cage-cross-linked polymers therefore represent a
platform for the development of new multifunctional materials.
1. J. A. Foster, R. M. Parker, A. M. Belenguer, N. Kishi, S. Sutton, C. Abell and J. R. Nitschke, J. Am.
Chem. Soc., 2015, 137, 9722. 2. T. Faust, Nat. Chem., 2015, 7, 681.
P25: Self-assembly formation of a healable lanthanide luminescent supramolecular metallogel from 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) ligands Eoin P. McCarney, Joseph P. Byrne,
a Brendan Twamley, Miguel Martínez-Calvo, Gavin Ryan, Jonathan Kitchen,
Matthias E. Möbius and Thorfinnur Gunnlaugsson*
Trinity Biomedical Sciences Institute and School of Chemistry, Trinity College, Dublin, Ireland., [email protected]
Abstract: Lanthanide (Ln(III)) ions are ideal for template-directed generation of novel functional
nanomaterials such as gels.[1] Self-healing of supramolecular polymers is an increasingly topical area of
research within supramolecular chemistry[1,2] with host−guest chemistry playing a significant role. We have
combined the ‘guest’ ability of Ln(III) ions with the versatile btp ‘host’ in the design of healable soft
matter.[3] Five new btp ligands were synthesised; the self-assembly behaviour of the tri-methyl ester, 1,
with Eu(III) showed the formation of a luminescent 1:3 Eu:btp complex, Eu13, while the tri-carboxylic acid,
2, formed a hydrogel and its corresponding Ln(III) complexes, Eu23 and Tb23, gave rise to strongly
luminescent healable metallogels in CH3OH Work is ongoing in tuning the luminescence of mixed Ln(III)
systems towards healable white light emitting gels.
1. M. Martínez-Calvo, O. Kotova, M. E. Möbius, A. P. Bell, T. McCabe, J. J. Boland and T. Gunnlaugsson, J. Am.
Chem. Soc., 2015, 137, 1983; (b) W. Weng, J. B. Beck, A. M. Jamieson and S. J. Rowan, J. Am. Chem. Soc., 2006, 128, 11663.
2. (a) G. Fiore, S. J. Rowan, C. Weder, Chem. Soc. Rev. 2013, 42, 7278; (b) X. Yu, L. Chen, M. Zhang, T. Yi, Chem. Soc. Rev. 2014, 43, 5346.
3. E. P. McCarney, J. P. Byrne, B. Twamley, M. Martinez-Calvo, G. Ryan, M. E. Möbius and T. Gunnlaugsson, Chem. Commun., 2015, 51, 14123.
P26: Protein Surface Recognition Using Functionalised Ruthenium (II) Tris(Bipyridines) S. H. Hewitt, A. J. Wilson University of Leeds, Leeds, LS2 9JT [email protected]
Abstract: Protein surfaces are notoriously difficult to recognise, often having few discernable features. One
way to recognise protein surfaces is the surface mimetic approach, whereby a functionalised
supramolecular structure is used to project multiple recognition groups over a large area of protein surface.
One such supramolecular structure is an inert, peripherally functionalised, ruthenium tris(bipyridine) core;
synthesis and binding of these molecules to a model protein, cytochrome c, have been established.1,2
Figure 1
An alternative means to use these molecules for proteins surface recognition is to exploit dynamic
combinatorial chemistry. This presentation will described the design and synthesis of a hydrazide
functionalised ruthenium tris(bipyridine) complex which can be reacted with mixtures of aldehydes under
equilibrium conditions, to identify hydrazine linked receptors for proteins (Figure 1).
1. J. Muldoon, A. E. Ashcroft, and A. J. Wilson, Chem. A Eur. J., 2010, 16, 100–3. 2. M. H. Filby, J. Muldoon, S. Dabb, N. C. Fletcher, A. E. Ashcroft, and A. J. Wilson, Chem. Commun., 2011, 47,
559–61.
RuNN
N
N
N
N
O
NH
O
HN
H2N
O
NH
O
HNNH2
O
HN
ONH
H2N
RuNN
N
N
N
N
O
NH
O
HN
N
O
NH
O
HNN
O
HN
ONH
N
H2Ncat.
O
mixture of
P27: LnIII-antenna scaffolds for functional soft polymer materials acting as luminescent logic gate mimics S. J. Bradberry,a J. P. Byrne,a C. P. McCoy,b R. D. Peacock,c T. Gunnlaugssona a School of Chemistry, Trinity Biomedical Science Institute (TBSI), Trinity College Dublin, Ireland;
b School of
Pharmacy, Queen’s University Belfast, UK; c School of Chemistry, University of Glasgow, Glasgow, UK
[email protected]; [email protected]
Abstract: Luminescent lanthanide complexes have been extensively employed in numerous fields of chemical and physical science.1,2 Privileged photophysical properties of ions such as EuIII, TbIII, NdIII and YbIII can be accessed using the versatile and extensive coordinating chromophores. The nature of coordination sphere of 4f-metals is substantially influenced by these peripheral organic structures. Diversity in the organic moieties of ligands allows for targeted control of complex stability, geometry, inner-sphere coordination and subsequent photophysical properties3 making use of such classes of compound a powerful approach to sensing. However, application and deployment of these functionalities as technologies in many research, industrial or commercial contexts demands appropriate materials platforms4,5 or advanced formulation6 to support, enhance and direct uses. When met, these demands allow generation of new devices that remain economically, environmentally and technologically relevant.
Herein, we present our most recent research into soft materials that are functionally enabled to respond to their environments, with luminescence changes.3a, 5 A family of readily accessible scaffolds are presented which exploit supramolecular, electron transfer and chiroptical properties and mimic logic functions. Simple device development for luminescent reporting demonstrates a route to non-covalent functionalised soft polymer gels. A cost-effective functional material is described which, using low loading of specialist compound, is manufactured and readily-processed into devices capable of analyte reporting and environmental response.
1. J.-C. G. Bünzli, J. Coord. Chem., 2014, 67, 3706. 2. (a) S. J. Bradberry, A. J. Savyasachi, M. Martinez-Calvo and T. Gunnlaugsson, Coord. Chem. Rev., 2014, 273–274,
226; (b) S. Comby, M. Surender, O. Kotova, L. K. Truman, J. K. Molloy and T. Gunnlaugsson, Inorg. Chem., 2014, 53, 1867.
3. (a) S. J. Bradberry, A. J. Savyasachi, R. D. Peacock and T. Gunnlaugsson, Faraday Discuss., 2015, in press; (b) O. Kotova, S. Blasco, B. Twamley, J. O'Brien, R. D. Peacock, J. A. Kitchen, M. Martinez-Calvo and T. Gunnlaugsson, Chem. Sci., 2015, 6, 457; (c) G. Muller, Dalton Trans., 2009, 9692.
4. (a) C. P. McCoy, F. Stomeo, S. E. Plush and T. Gunnlaugsson, Chem. Mater., 2006, 18, 4336; b) T. Gunnlaugsson, C. P. McCoy and F. Stomeo, Tetrahedron Lett., 2004, 45, 8403; c) K. Binnemans, Chem. Rev., 2009, 109, 4283.
5. S. J. Bradberry, J. P. Byrne, C. P. McCoy and T. Gunnlaugsson, Chem. Commun., 2015, 51, 16565. 6. J. Andres, R. D. Hersch, J.-E. Moser and A.-S. Chauvin, Adv. Funct. Mater., 2014, 24, 5029.
P28: Effect of concentration on high pressure/ low temperature polymorphism R. Lee, A. J. Firbank, M. R. Probert, J. W. Steed Department of Chemistry, Durham University, South Rd, Durham, UK DH1 3LE [email protected]
Abstract:
Polymorphism at high pressure is a concept which has been gaining interest, with drastic improvements in
the equipment available over the past few decades; it is becoming a more common way to map a crystals
structural and polymorphic landscape.1 It is possible to predict whether or not a substance or mixture
possess high pressure/low temperature polymorphism based on the potential bonding types of a molecule,
and the crystal packing if a structure is known already. In order to better understand the subtleties which
contribute to this type of polymorphism, mixtures of pyridine and formic acid were investigated using both
diamond anvil cell and capillary crystallization techniques.
Pyridine and formic acid are
known to form co-crystals at
low temperature, in the ratios
1:1 and 1:4. 2 Interestingly,
one of these is a molecular
crystal, while the other
contains ionic components.
Two novel structures have
been found from high pressure; a previously unknown 1:2 salt co-crystal, and a new polymorph of the 1:4
mixture. Pyridine-formic acid is a system which displays a strong O-HN hydrogen bond, however the
degree of proton transfer can be manipulated by the addition of further equivalents of formic acid; as the
relative concentration of polar components increases, the O-HN bond gradually increases in strength
until proton transfer occurs. This results in a system with different bonding types and motifs to the original
system, which has a significant effect on the high pressure/low temperature polymorphism of this series.
1. R. Lee, J. A. K. Howard, M. R. Probert and J. W. Steed, Chem. Soc. Rev., 2014, 43, 4300-4311.
2. D. Wiechert and D. Mootz, Angew. Chem.-Int. Edit., 1999, 38, 1974-1976.
P29: Tripodal tris(urea) propellers for anion binding and self-assembly A. Aletti, S. Blasco, C. S. Hawes, A. J. Savyasachi, T. Gunnlaugsson
School of Chemistry and Trinity Biomedical Sciences Institute, Trinity College Dublin, Ireland. [email protected]; [email protected]
Abstract: The field of anion receptors and binding has received focussed attention in recent years due to
their biological and environmental relevance.1 Additionally, the appropriate design of ligands can exploit
the binding abilities of anions to create self-assembled architectures such as cages, capsules and
interlocked systems.2 The results presented herein explore the binding abilities of set of novel benzene
1,3,5-tricarboxamide (bta) based3 tripodal tris(urea) receptors that were investigated for the formation of
supramolecular self-assembled structures and to understand their properties.
Four tripodal ligands were synthesised from the central core via amide couplings to N-methyl-3-nitroaniline
followed by condensation with various electron deficient phenyl isocyanates. The tris(urea) ligands were
structurally characterised in solution and as single crystals; these are presented alongside their solution
binding properties (with Cl-, H2PO4-, AcO- and SO4
2-) by UV-vis and NMR techniques revealing behaviour as
discrete receptors in competitive media.
Binding modes and stability constants (logβ) are elucidated by regression analysis of UV-vis and NMR
titration data in both DMSO and CH3CN from which it is shown that various behaviours and selectivity
emerge under different solvent conditions. The concentration dependence of these receptor properties are
characterised and the resultant solution and solid-state formations probed by spectroscopic and scanning
electron microscopy (SEM) techniques.
1. N. Busschaert, C. Caltagirone, W. Van Rossom and P. A. Gale, Chem. Rev., 2015, 115, 8038-8155. 2. K. Pandurangan, J. A. Kitchen, S. Blasco, E. M. Boyle, B. Fitzpatrick, M. Feeney, P. E. Kruger and T.
Gunnlaugsson, Angew. Chem. Int. Ed., 2015, 54, 4566-4570. 3. C. M. dos Santos, E. M. Boyle, S. De Solis, P. E. Kruger and T. Gunnlaugsson, Chem. Commun., 2011, 47,
12176-12178.
P30: Synthetic Macromolecules Capable of Recognition Clare S. Mahon and David A. Fulton* Chemical Nanoscience Laboratory, School of Chemistry, Newcastle University, NE1 7RU [email protected]
Abstract: At Newcastle we have developed the so-called Polymer-Scaffolded Dynamic Combinatorial
Library (PS-DCL) concept1 as a method for the discovery of synthetic macromolecules capable of molecular
recognition.2 PS-DCLs are constructed (figure 1) in aqueous solution by the grafting of functionalized
acylhydrazide residues onto a pre-formed polymer scaffold through dynamic hydrazone bonds, where the
reversibility of these bonds allows residues to exchange and reshuffle their positions upon the polymer
scaffold. The addition of macromolecular templates to PS-DCLs induces significant constitutional
reorganization, with polymer chains selecting those residues which promote strong binding and discarding
those which do not. The best binding polymers can then be isolated and their binding properties assayed.
In this presentation we will demonstrate the potential of the PS-DCL concept, using a variety of protein and
synthetic polymer templates to prepare macromolecules with enhanced capabilities for molecular
recognition.
Figure 1. The reversible conjugation of various acylhydrazides onto an aldehyde-functionalised polymer scaffold affords a library of structurally interconverting polymers (a Polymer-Scaffolded Dynamic Combinatorial Library). Addition of a macromolecular template induces re-equilibration of the system, with polymer scaffolds preferentially incorporating residues which interact favourably with the template. The best-binding fraction of the library is then isolated and assayed.
1 C. S. Mahon and D. A. Fulton, Nature Chem. 2014, 6, 665-672. 2 C. S. Mahon, and D. A. Fulton Chem. Sci. 2013, 4, 3661-3666.
elf here. Do not
alter the size of
the box
(2.5x2.5cm)
P31: Novel europium complexes as pH-sensitive, lysosome-selective luminescent probes Sergey Shuvaev, Robert Pal, David Parker Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK [email protected]
Targeted imaging of selected organelles within the cells is a prerequisite towards a better understanding of
certain biochemical processes occurring in living organisms. The lysosomes, responsible for digesting worn-
out organelles, engulfed bacteria, viruses and other potentially harmful particles, play a crucial role in
several diseases (e.g. lysosomal storage diseases) that are caused by malfunction of certain digestive
enzymes. However, only a few examples of lysosome-targeted probes have been reported. Such probes
can help to gain deeper insight into the functioning of lysosomal enzymes, or allow the cell’s response to
new drugs to be assessed.
The pH value inside a lysosome (range 6.5 to 4.6) differs considerably from that in the surrounding cytosol
(7.2) and other organelles. A pH-sensitive probe needs to operate therefore in the pH range 4 to 7, and
should be signalled by a change in the ratio of emission intensities or of emission lifetime. We have recently
reported strategies for this purpose using azaxanthone chromophores in 12-N4 systems 1, and have devised
brighter complexes, derived from triazacyclononane, that report pH in the endoplasmic reticulum. 2
The target cyclen-based structural core bears different N-substituents (Fig. 1). The first group is anionic and
binds strongly to the Eu(III) centre; the second bidentate moiety imparts structural rigidity to the
coordination sphere around europium and serves as the chromophore allowing efficient excitation in the
near-UV region, along with wide opportunities for further structural modification by introducing electron-
donating or electron-withdrawing groups. The sulfonamide moiety binds reversibly to the metal centre as a
function of pH, thereby modulating the intensity of europium emission. The final site may be unsubstituted
or can be linked to a targeting vector for recognition by, for example, the lysosomal membrane.
Figure 1
1. D. G. Smith, B. K. McMahon, R. Pal, D. Parker, Chem. Commun., 2012, 48, 8520. 2. B. K. McMahon, R. Pal, D. Parker, Chem. Commun., 2013, 49, 5363.
Please include a
300 dpi picture of
yourself here. Do
not alter the size
of the box
(2.5x2.5cm)
P32: The Dynamic Covalent Rearrangements of Barbaralyl Cations Aisha N. Bismillah, Gemma L. Parker & Paul R. McGonigal* The University of Durham, Department of Chemistry, Science Site, South Road, DH1 3LE [email protected]
Abstract:
Shapeshifting molecules[1], in which low-energy rearrangements bring about the rapid interconversion of
hundreds of distinct regioisomers, have the potential to address challenges in binding and detecting
specific ions, complex small molecules and macromolecules. The shapeshifting 9-barbaralyl cation, is an
impressively fluxional C9H9+ hydrocarbon that exists as mixture of 181 400 degenerate forms,
interconverting rapidly through dynamic covalent rearrangements at temperatures as low as – 135 °C. It
has been reported[2] recently that gold-catalysed isomerisation of simple alkynyl cycloheptatrienes (e.g., 1),
leads to indene products after first passing through barbaralyl cation intermediates. Employing this gold-
catalysed transformation, we are targeting stabilised, shapeshifting barbaralyl cations. We present
preliminary synthetic and spectroscopic investigations into the nucleophilic trapping of substituted
barbaralanes (e.g., 3), by the addition of methanol to reactive barbaralyl–gold intermediates (e.g., 2).
Figure 2. A synthetic approach to (±)(1R,5S,8R,9S)-9methoxy-4-(naphthalen-2-yl)tricycle[3.3.1.02,8]nona-
3,6-diene (3) through the gold-catalysed activation of 2-(cyclohepta-2,4,6-trien-1-ylethynyl)naphthalene
(1) and entrapment through methanol.
1. J. F. Teichert, D. Mazunin and J. W. Bode, J. Am. Chem. Soc., 2013, 135, 11314–11321. 2. P. R. McGonigal, C. de León, Y. Wang, A. Homs, C. R. Solorio-Alvarado and A. M. Echavarren, Angew. Chem.
Int. Ed., 2012, 51, 13093–13096.
P33: New Ruthenium(II) Polypyridyl Complexes as Promising PDT Agents and Luminescent Probes for DNA in HeLa Cells Bjørn la Cour Poulsen, Sandra Estalayo-Adrián, Salvador Blasco, Sandra A. Bright, Robert B. P. Elmes, Fergus E. Poynton, D. Clive Williams and Thorfinnur Gunnlaugsson Trinity Biomedical Science Institute, Trinity College Dublin, University of Dublin, 152-160 Pearse St, Dublin 2, Ireland [email protected], [email protected]
Abstract: Since the discovery of cisplatin and its well-known antitumor effect, the development of novel
metal-based therapeutic agents has become a topic of great interest.1,2 Ruthenium(II) polypyridyl
complexes are promising candidates in this area due to their interesting photophysical, photochemical and
redox properties.3 In particular, those containing extended aromatic ligands such as dipyrido[3,2-a :2’,3’-
c]phenazine (dppz) display photo-switchable luminescent and intercalation properties towards DNA.4
In this work, we report a family of Ru(II) polypyridyl complexes with new extended ligands derived from
dppz along with studies of their ability to bind to DNA using different spectroscopic techniques. Their
possible application as photodynamic therapeutic (PDT) agents is also evaluated in HeLa cervical cancer
cells and confocal microscopy is used to study the uptake in vitro.
All the complexes bind strongly to DNA with binding constants in the order of 106 M-1. Ru(II) complexes
containing phen as ancillary ligands have displayed the well-known "light-switch" effect upon interaction
with DNA.5 Moreover, Ru(II) complexes with TAP have shown a good therapeutic window as PDT agents in
HeLa cells with IC50 values about 4 μM in light and IC50 values about 60 μM in dark.
1 B. Rosenberg, L. Van Camp, T. Krigas, Nature, 1965, 205, 698-699. 2 Medicinal Organometallic Chemistry, G. Jaouen, N. Metzler-Nolte (eds.), Berlin Heidelberg: Springer, 2010. ISBN 978-3-642-13184-4 3 V. Balzani, A. Juris, M. Venturi, S. Campagna, S. Serroni, Chem. Rev., 1996, 96, 759-833. 4 S. M. Cloonan, R. B. P. Elmes, M.L. Erby, S. A. Bright, F. E. Poynton, D. E. Nolan, S. J. Quinn, T. Gunnlaugsson, D. C. Williams, J. Med. Chem., 2015, 58, 4494-4505. 5 Y. Jenkins, A. E. Friedman, N. J. Turro, J. K. Barton, Biochemistry, 1992, 31, 10809-10816.
P34: A New Reversible 1,3-Dipolar Cycloaddition and its Application in Dynamic Covalent Chemistry David van Brussel and Douglas Philp* EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, United Kingdom [email protected]
For chemists, increasing the conversion, rate and selectivity of chemical reactions is of great interest. One
way to achieve these goals is to design a recognition-mediated reaction pathway in which the reagents
associate through non-covalent interactions prior to reacting.1 The association of the starting materials
through non-covalent interactions can lower the kinetic barrier of the chemical reaction as the process that
now takes place is pseudo-intramolecular.2,3 Furthermore, the non-covalent interactions will live on in the
product of the chemical reaction, which offers the product additional thermodynamic stability and, thus,
conversion can increase.3 The 1,3-dipolar cycloaddition between a nitrone and a 2-arylidine-1,3-indandione
is a reversible and unfavourable reaction. However, the conversion and selectivity of the reaction can be
greatly influenced when the starting materials are equipped with complementary recognition sites.
Interestingly, the position of the recognition sites relative to the reactive site on the nitrone has a
remarkable influence on the conversion and the selectivity of this cycloaddition.
Dynamic covalent libraries (DCLs) are constructed from building blocks that can react reversibly to afford a
mixture of library constituents under thermodynamic control. Non-covalent interactions have been used to
select one member of the DCL and amplify this member at the expense of the other library constituents.4
Similarly, a library was created using indandiones and nitrones equipped with complementary recognition
sites in which a dramatic enhancement of one of the diastereometric cycloadducts was observed compared
to the reaction in isolation. This poster reports on the recognition-mediated facilitation of the 1,3-dipolar
cycloaddition and its application in the construction of a DCL.
1 M. Raynal, P. Ballester, A. Vidal-Ferran, P. W. N. M. van Leeuwen, Chem. Soc. Rev., 2014, 43, 1734-1787. 2 M. I. Page, W. P. Jencks, Proc. Natl. Acad. Sci. USA, 1971, 68, 1678-1683. 3 R. Bennes, D. Philp, N. Spencer, B. M. Kariuki, K. D. M. Harris, Org. Lett., 1999, 1, 1087-1090. 4 J. Li, P. Nowak, S. Otto, J. Am. Chem. Soc., 2013, 135, 9222-9239.
P35: Complementary Dynamic Covalent Nanoparticle Building Blocks Nicolas Marro and Euan R. Kay EaStCHEM School of Chemistry, University of St Andrews, Fife, KY16 9ST, UK [email protected]
Abstract: Nanoparticles (NPs) are known for their unique electrical, optical, physical and chemical properties,1 which are closely correlated with their structural aspects: core material, size, shape, and surface-bound molecular species. All emerging or proposed applications for nanomaterials will require the integration of NPs with each other, with molecules, or with micro and macroscopic components. Most of the available approaches for NP functionalization rely on noncovalent interactions, particularly between oligonucleotide ligands.2 However, these interactions are extremely sensitive to environmental conditions and the structural scope is limited by requiring complex biomolecules. Only rudimentary covalent bond forming reactions have been carried out on molecules confined to nanoparticle surfaces, almost exclusively operating under kinetic control.3 Dynamic covalent chemistry provides an alternative approach for post-synthetic NPs functionalization, which would combine reversibility and the intrinsic stability of covalent bonds. Recently, the first example of dynamic covalent hydrazone exchange occurring on monolayer-stabilized gold NPs was demonstrated, and applied to reversibly control NP properties.4 In this previous work, the nucleophilic end (hydrazide) of an exchangeable hydrazone was attached to the NP surface (Fig A). Here we present the complementary family of dynamic covalent nanoparticles (DCNPs), in which the electrophilic (carbonyl) component is attached to the NPs surface, and demonstrate NP-bound dynamic covalent hydrazone exchange using nucleophilic exchange units (Fig B). Access to both families of DCNPs significantly widens the scope of this strategy for postsynthetic NP functionalization. We also report preliminary results on the self-assembly of the two complementary set of DCNPs under thermodynamically controlled hydrazone exchange conditions (Fig C).
1 S. E. Lohse and C. J. Murphy, J. Am. Chem. Soc., 2012, 134, 15607-15620. 2 S. Y. Park, A. K. R. Lytton-Jean, B. Lee, S. Weigand, G. C. Schatz and C. A. Mirkin, Nature, 2008, 451, 553-556. 3 K. E. Sapsford, W. R. Algar, L. Berti, K. B. Gemmill, B. J. Casey, O. Eunkeu. M. H. Stewart and I. L. Medintz, Chem.
Rev., 2013, 113, 1904–2074. 4 F. della Sala, E. R. Kay, Angew. Chem. Int. Ed., 2015, 54, 4187-4191.
A B
C
First generation hydrazone-based DCNPs Hydrazone-based DCNPs self-assembly
Complementary hydrazone-based DCNPs
P36: Synthesis of metal clusters and Tröger’s base derivatives of 4-(aryl)-2,2’-bipyridine-6-carboxylic acid Hannah L. Dalton, Chris S. Hawes, Thorfinnur Gunnlaugsson. School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, Ireland. [email protected]
Abstract: Custom designed supramolecular assemblies have been an area of intense research because of
their potential applications in a wide range of disciplines within the chemical and material sciences.
Substantial progress has been made from the exploration of a range of heterotopic chelating ligand species,
due to their favourable metal binding properties and modular syntheses.1 The synthesis of a family of
tridentate ligands of the type 4-(aryl)-2,2’-bipyridine-6-carboxylic acid and their coordination chemistry to
transition metal and lanthanide ions was explored to yield metal clusters of varying nuclearity. Their
structural and physical properties have been examined as precursors towards new functional
metallosupramolecular materials.2 Moreover, these versatile precursors have been carried forward to
quarternized bipyridine analogues conjugated via a phenyl spacer to a 4-amino-1,8 -naphthalimide derived
Tröger’s base.3 From the preliminary photophysical evaluation of these materials and the activity of related
compounds, such materials are envisioned to display DNA intercalation properties based on a combination
of electrostatic and geometric considerations. 4
1. J. P. Byrne, J. A. Kitchen and T. Gunnlaugsson, Chem. Soc. Rev, 2014, 43, 5302-5325. 2. J. P. Byrne, J. A. Kitchen, O. Kotova, V. Leigh, A. P. Bell, J. J. Boland, M. Albrecht and T.
Gunnlaugsson, Dalton Trans., 2014, 43, 196-209. 3. G. J. Ryan, R. B. P. Elmes, S. J. Quinn and T. Gunnlaugsson, Supramol Chem., 2012, 24, 175-
188. 4. R. B. P. Elmes, M. Erby, S. A. Bright, D. C. Williams and T. Gunnlaugsson, Chem Comm.,
2012, 48, 2588-2590.
P37: Coordination chemistry and photophysical properties of bis(pyrazolyl-pyridine) ligands: From mono-nuclear to the supramolecular
Zainab N. Zubaidi, and Michael D. Ward Department of Chemistry, University of Sheffield, Sheffield S3 7HF, U.K. E-mail: [email protected] , and [email protected].
Abstract
New dinuclear complexes containing a combination of a chromophoric transition metal unit
(iridium/phenylpyridines) were combined with a lanthanide unit (europium, terbium and gadolinium) to
create Ir(III)/Ln(III) dyads (fig. 1).1,2 These complexes show luminescence at two different wavelengths and
on two different timescales following Ir-Eu or Ir-Tb energy-transfer.
Figure (1) Molecular structures of (F2PhPy and MePyPy) iridium complexes.
This study contains a mixture of inorganic synthesis, characterisation and coordination chemistry of new
complexes, and photophysical measurements with the aim of cell imaging using confocal microscopy to
evaluate the performance of the new complexes.
References:
1- D. Sykes, S. C. Parker, I. V. Sazanovich, A. Stephenson, J. A. Weinstein, and M. D. Ward, Inorg. Chem. 2013, 52, 10500-10511.
2- E.Baggaley, D.K. Cao, D. Sykes, S.W.Botchway, J. A. Weinstein, and M. D. Ward, Chem. Eur. J. 2014, 20, 8898-8903.
P38: Anion binding of the m-phenylene bis(phenylurea) motif Dermot Gillen, Chris S. Hawes, Salvador Blasco and Thorfinnur Gunnlaugsson School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, 152 - 160 Pearse Street, Dublin 2, Ireland [email protected]
Abstract: Anion host-guest chemistry has developed into a wide-ranging field with such
applications as anion sensors, responsive gels and transporter molecules.1 Of particular interest
are ureas, which bind many anions but exhibit complementary interactions with carboxylates. We
have previously reported several examples of urea-based anion receptors demonstrating PET and
allosteric effects.2 This understanding has led to more complex structures such as clefts, cages and
tripodal structures which bind other anions such as phosphates in various media.3
We have synthesised a family of small compounds derived from the 1,1’(1,3-phenylene)bis(3-
phenylurea) core which frustrate the natural affinity similar urea motifs have for carboxylates.4
This is expected to lead to a higher selectivity for phosphates. The anion-binding properties of
these compounds have been analysed in solution and through their crystalline adducts.
Examination of these adducts shows ineffective acetate binding, and the formation of
multicomponent assemblies with phosphates.
1. N. Busschaert, C. Caltagirone, W. Van Rossom and P. A. Gale, Chem Rev, 2015, 115, 8038-8155. 2. C. M. dos Santos, T. McCabe, G. W. Watson, P. E. Kruger and T. Gunnlaugsson, J. Org. Chem., 2008, 73, 9235-
9244.; T. Gunnlaugsson, P. E. Kruger, T. C. Lee, R. Parkesh, F. M. Pfeffer and G. M. Hussey, Tet. Lett., 2003, 44, 6575-6578.
3. E. M. Boyle, S. Comby, J. K. Molloy and T. Gunnlaugsson, J. Org. Chem., 2013, 78, 8312-8319.; K. Pandurangan, J. A. Kitchen, S. Blasco, E. M. Boyle, B. Fitzpatrick, M. Feeney, P. E. Kruger and T. Gunnlaugsson, Angew. Chem. Int. Ed., 2015, 54, 4566-4570.; C. M. dos Santos, E. M. Boyle, S. De Solis, P. E. Kruger and T. Gunnlaugsson, Chem. Commun., 2011, 47, 12176-12178.
4. S. J. Brooks, P. R. Edwards, P. A. Gale and M. E. Light, New J Chem, 2006, 30, 65-70.
P39: Dynamic Covalent Tuning of Nanoparticle Properties William Edwards, Grace Turner and Euan R. Kay* School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK [email protected]
Abstract: Ligand protected nanoparticles (NPs) have huge potential in fields such as catalysis, medicine and sensing.1 Whilst their nanometre-scale cores are responsible for many of their unique properties, the surrounding ligand monolayer can also play a crucial role in determining overall behaviour.2 Not only do the ligands provide colloidal stability but they can also contribute to functionality themselves, for example, mediating recognition, bioactivity and interactions with light. Impressive control over modification of NP-bound ligands has been demonstrated using oligonucleotides3 but their inherent fragility limits these systems to a small area of chemical space. Other common approaches to ligand modification also have significant drawbacks.2
We propose that dynamic covalent chemistry (DCC) can be a solution to this challenge.4, 5 Labile covalent bonds can be used to reversibly modify the ligand shell and then a change in conditions can render the product kinetically fixed, allowing purification and characterisation of the resultant NPs. This approach should allow us to bring to bear a vast range of reactions and structures to modify the surface ligands in a way that is relatively unaffected by the underlying core material.
Here, building on previous work,4 we will demonstrate how a simple dynamic covalent reaction – hydrazone exchange – is affected by nanoparticle design. We will also show that systematic variation of the ligand monolayer can result in NPs with a continuum of properties, in this case, varying colloidal stability in solvent ranging from hexane to water.
1 M.-C. Daniel and D. Astruc, Chem. Rev., 2004, 104, 293-346. 2 W. Edwards and E. R. Kay, ChemNanoMat, 2015, DOI: 10.1002/cnma.201500146 3 E. Auyeung, T. I. N. G. Li, A. J. Senesi, A. L. Schmucker, B. C. Pals, M. O. de la Cruz, C. A. Mirkin Nature,
2014, 505, 73-77. 4 F. della Sala and E. R. Kay, Angew. Chem. Int. Ed., 2015, 54, 4187-4191. 5 P. Nowak, V. Saggiomo, F. Salehian, M. Colomb-Delsuc, Y. Han and S. Otto, Angew. Chem. Int. Ed., 2015,
54, 4192-4197.
P40: Lamellar urea tape networks as building blocks for crystals and gels C. D. Jones and J. W. Steed Department of Chemistry, Durham University, South Road, Durham. DH1 3LE. [email protected]
Abstract: Molecules containing two or more urea (-NHCONH-) functional groups often exhibit an
exceptional capacity for gel formation, due to their tendency to form highly anisotropic networks of
hydrogen bonding tape motifs.1 The single-crystal structures of one series of sterically hindered bis-ureas
display seven different network topologies, of which just four have been reported previously. Intriguingly,
two-dimensional networks are common only among the bis-ureas derived from primary amines, which
account for all observed instances of gel formation. Powder diffraction studies indicate that gels of these
compounds are also composed of lamellar assemblies, and molecular dynamics simulations confirm that
such monolayers may, in isolation, afford fibrous aggregates through spontaneous scrolling about the tape
axis. This mode of aggregation is favoured by lamellae that are facially asymmetric, in solvent environments
that lower the energy of the dominant faces and thus limit the potential for three-dimensional growth. The
simulated outcome of folding – an unbranched radially isotropic fibre with a diameter dictated by the
minimum lamellar curvature – is consistent with scanning electron micrographs of the dried gels. Helically
twisted lamellae may also be possible, however, if self-assembly involves a variety of tapes oriented along
non-orthogonal axes. Structures of this type were observed in gels of linear achiral tris- and oligo-ureas,
and found to resemble the cross-β sheet assemblies of amyloid proteins.2 The fibres are typically narrow
and monodisperse, and intertwine to form braids in well-defined periodic configurations, providing a useful
synthetic analogue of the ordered hierarchical aggregates found in biological systems.
1. J. W. Steed, Chem. Soc. Rev., 2010, 39, 3686-3699. 2. W. Dzwolak, Chirality, 2014, 26, 580-587.
P41: Crystalline Supramolecular Rotors Assembled through Halogen-Bonding Luca Catalano,1 Salvador Pérez-Estrada,2 Giancarlo Terraneo,1 Tullio Pilati,1 Giuseppe Resnati,1 Pierangelo Metrangolo1,3 and Miguel Garcia-Garibay2
1 NFMLab – DCMIC “Giulio Natta”, Politecnico di Milano, Milan, Italy 2 Department of Chemistry and Biochemistry, UCLA, Los Angeles, USA 3 VTT-Technical Research Centre of Finland, Espoo, Finland [email protected]
Abstract We present a modular strategy for the preparation of multi-component crystalline supramolecular rotors from a set of simple and commercially available stators and rotators, which can trivially yield to a vast number of supramolecular species and to a fine control of their molecular dynamics and other interesting physical properties.1
In particular we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicylo[2.2.2]octane (DABCO), acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. We first characterized the adducts via single crystal XRD, IR spectroscopy and melting point measurements to confirm their formation. Then we used variable temperature 1H T1 spin lattice relaxation measurements to characterize the molecular dynamics of the rotors. All structures display ultrafast Brownian rotation with activation energies ranging from 2.4 to 4.9 kcal/mol and pre-exponential factors of the order of 1–9 x 1012 s-1. Lineshape analysis of quadrupolar echo 2H NMR measurements in selected examples indicated rotational trajectories consistent with both 3-fold and 6-fold symmetric potential of the rotator.2
Figure 1. The schematic structure of a supramolecular crystalline rotor obtained by mixing iodopentafluorobenzene and DABCO in 2:1 molar ratio.
1. C.S. Vogelsberg, M. Garcia-Garibay, Chem. Soc. Rev., 2012, 41, 1892-1910. 2. L. Catalano, S. Pérez-Estrada, G. Terraneo, T. Pilati, G. Resnati, P. Metrangolo, M. Garcia-Garibay, J. Am. Chem. Soc.,
2015, accepted manuscript.
P42: Asymmetric Catalysis with Rotaxane Atropisomer Sündüs Erbaş-Çakmak, Yusuf Çakmak, David A. Leigh* School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK [email protected]
Abstract: Mechanically interlocked molecules can have unique structural and chemical properties enabling construction of complicated molecular devices and machines, including their use as supramolecular catalysts.1-4 Enantioselective and regioselective catalysis with rotaxanes are reported previously, each benefitting either from chiral auxillaries or sterics of rotaxane structures.5-7 In this work we have shown that with sole mechanical bonding, point chirality can be created on an otherwise achiral carbon center and this created spatial asymmetry around the neighboring amine catalyst on the thread of the rotaxane can be used for asymmetric catalysis. Chemical structures of the rotaxane (S)-1 and achiral free thread T1 are shown in Figure 1. Supramolecular interaction (hydrogen bonding) between the macrocycle and one of the succinamide stations of the thread breaks the symmetry around the prochirality center, Cx. A bulky p-xylylamine barrier restricts macrocycle shuttling between degenerate stations, thus allows generation of stable enantiomers of the rotaxane catalyst. With this mechanochirogenesis, enantioselective catalysis via both enamine and iminium activation modes are successfully demonstrated (Figure 1b).
Figure 1. Chemical structure of rotaxane catalyst (S)-1 and thread T1. Mechanically generated point chirality
on Cx is highlighted (a). Enantioselective catalysis with (S)-1 is demonstrated by Michael addition to ,-
unsaturated aldehydes (iminium activation mode) and -amination of aldehydes (enamine activation
mode) (b).
1 S. Erbas-Cakmak, D. A. Leigh, C. T. Mcternan, A. L. Nussbaumer, Chem. Rev., 2015, 115, 10081-10206. 2 E. A. Niel, S. M. Goldup, Chem. Commun. 2014, 50, 5128-5142. 3 V. Blanco, D. A. Leigh, V. Marcos, Chem Soc. Rev. 2015, 44, 5341-5370. 4 D. A. Leigh, V. Marcos, M. R. Wilson, ACS Catal. 2015, 4, 4490-4497. 5 Y. Tachibana, N. Kihara, T. Takata, J. Am. Chem. Soc. 2004, 126, 3438-3439. 6 V. Blanco, D. A. Leigh, V. Marcos, J. A. Morales-Serna, A. L. Nussbaumer, J. Am. Chem. Soc. 2014, 136,
4905-4908. 7 M. Galli, J. E. M. Lewis, S. M. Goldup, Angew. Chem. Int. Ed. 2015, 54, 13545-13549
a)
b)
P43: Towards Directional Small Molecule Walker Yusuf Çakmak, Tuba Yaşar, Sündüs Erbaş-Çakmak, David A. Leigh*
University of Manchester, School of Chemistry, Dover Street, Manchester, UK, M13 9PL [email protected]
Abstract: Molecular motors are used extensively in biology. By driving the chemical
systems away from equilibrium vital tasks are performed such as transporting cargoes directionally and by
this way work is done. By ATP hydrolysis kinesin, myosin and dynein motor proteins are directionally driven
along microtubule or actin filament tracks.1 These are the fascinating examples from biology which
scientists inspired from. Leigh group has published various small molecule walker systems in recent years
that can successfully walk down a track either through random walk or sequential orthogonal biped
exchange.1-3 In order to achieve useful tasks; directionality of the walker should be achieved. Although
some efforts have been done, 1,2 an efficient unidirectional small molecule walker is yet to be made. In this
study we have used the basic principles of the first generation walker structure1 (orthogonal biped
exchange) and added functionalities in order to attain directional walking down the track. The feet of the
walker that we suggest composed of hydrazone (acid-labile) and (base-labile) linkages which are labile in
orthogonal conditions(Figure 1). And we have extra unit in the walker part for its interaction with the track.
This unit [bis(triethyleneglycol) structure] is able to interact with the ammonium and triazolium units and
this interaction can be modified by using acid and base in order to choose which station that we want it to
interact. Since both the binding of the interacting unit and the feet’s lability can be controlled by acid and
base we should be able to control the place of the walker in the track. By this way, we aim to achieve first
small molecule walker motor walking down the track directionally. The ultimate goal of ours is to produce
linear molecular motors moving directionally along polymeric tracks for transporting cargoes and
performing tasks similar to the biological motor proteins.
Figure 1. Chemical structure of the small molecule walker (top) and the schematic representation of the
directional walking process (down).
1. M. von Delius, E. M. Geertsema and D. A. Leigh, Nature Chem., 2010, 2, 96-101. 2. A. G. Campaña, D. A. Leigh and U. Lewandowska, J. Am. Chem. Soc., 2013, 135, 8639−8645. 3. J. E. Beves, V. Blanco, B. A. Blight, R. Carrillo, D. M. D’Souza, D. C. Howgego, D. A. Leigh, A. M. Z. Slawin and M. D. Symes, J. Am. Chem. Soc., 2014, 136, 2094–2100
base acid
P44: Thermoresponsive polymers for on/off lectin recognition Clare S. Mahon and W. Bruce Turnbull School of Chemistry and Astbury Centre for Structural Molecular Biology, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT [email protected]
Fig. 1 Thermoresponsive polymers may switch on or off their recognition behaviour towards cholera toxin
upon application of a thermal stimulus.
Thermoresponsive polymers have been prepared and decorated with multiple copies of carbohydrate units, enabling the production of multivalent receptors for carbohydrate-binding proteins (lectins). These polymers have been shown to recognise lectins, including the cholera toxin. Association constants determined to be of the order of 105 M-1 by isothermal titration calorimetry, presenting 1000-fold improvements in affinity compared to monovalent carbohydrates. At the lower critical solution temperature of the polymer, polymer chains undergo a reversible coil-to-globule transition which removes their ability to recognise their target protein. This thermally switchable recognition behaviour presents the opportunity for the development of ‘catch-and-release’ receptors for bacterial toxins.
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P45: Emergent Self-assembly of Porous Organic Cages Baiyang Teng and Andrew I. Cooper* Department of Chemistry and Centre for Materials Discovery, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK. [email protected]
Abstract: Self-assembled porous organic cages offer promising approaches to applications, such as gas
storage1 and molecular separation.2,3 Large multicomponent cages (with 20 components or more) present a
greater synthetic challenge, and there are limited examples of large cages with permanent porosity.4 Here,
we describe the synthesis of two new porous organic imine cage compounds that were prepared using
diamine subunits with the same chemical composition but that have different shapes (Figure 1, [4+6] and
[8+12]). The synthetic procedures of the two cages is described and indicates that the formation of the
[8+12] cage is more sensitive to experimental conditions. Both cages are proved to be porous to N2 at 77 K,
and a high apparent surface area of 1807 m2g-1 is obtained for the large [8+12] cage. Both cages are soluble
in organic solvents and show fluorescence emission, and a crystallographic study highlights that the [8+12]
cages shows certain range of “shape-flexibility” in the solid state whereas the [4+6] cage is rigid.
Figure 1. [4+6] cage and [8+12] cage
1 M. Mastalerz.; M. W. Schneider.; I. M. Oppel. and O. Presly. Angew. Chem. Int. Edit., 2011, 50, 1046-1051. 2 L. Chen.; P. S. Reiss.; S. Y. Chong.; D. Holden.; K. E. Jefts.; T. Hasell.; M. A. Little.; A. Kewley.; M. E. Briggs.; A.
Stephenson.; K. M. Thomas.; J. A. Armstrong.; J. Bell.; J. Busto.; R. Noel.; J. Liu.; D. M. Strachan.; P. K. Thallapally. and A.I. Cooper. Nat Mater 2014, 13, 954-960.
3 T. Mitra.; K. E. Jelfs.; M. Schmidtmann.; A. Ahmed.; S. Y. Chong.; D. J. Adams. and A.I. Cooper. Nat Chem 2013, 5, 276-281.
4 G. Zhang. and M. Mastalerz. Chem Soc Rev 2014, 43, 1934-1947.
P46: Molecular recogniton events by new multimetallic cages based on tris(2-pyridylmethyl)amine complexes Carlo Bravin,a Elena Badetti,a Francesca A. Scaramuzzo,a Rakesh Puttreddy,b Fangfang Pan,b Kari Rissanen,b Giulia Licini,a Cristiano Zonta,a Carlo Bravin, Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy [email protected]
a Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova
b Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland
Biological and synthetic molecular containers have largely attracted the attention of scientists for their
peculiar properties and applications.1 In particular, supramolecular capsules and cages have offered in
recent years the opportunity to draw important guidelines about the interpretation of the confination
phenomena. In this communication, we report the formation of a series of new self-assembled cages
containing, in the inner part of the cavity, two metals with a coordination site available for binding. We
have planned to take the advantage offered by dynamic covalent chemistry (DCC) for the synthesis of
molecular cages of opportunely designed tris(2-pyridylmethyl)amine TPMA metal complexes.2 TPMA
complexes are known to furnish stable species that have been previously used for carboxylic acids
recognition.3 The findings on their molecular recognition properties highlight unprecedented results in the
thermodynamic of binding events that have a broad impact in the understanding of the molecular
recognition phenomena in a wider context.
Figure 1 Synthesis and X-ray crystal structure of the tris(2-pyridylmethyl)amine cage
1. P. Ballester, M. Fujita, J. Rebek, Chem. Soc. Rev., 2015, 44, 392-393.
2. F. A Scaramuzzo, G. Licini, C. Zonta, Chem. Eur. J., 2013, 19, 16809-16813.
3. Joyce, L. A.; Maynor, M. S.; Dragna, J. M.; da Cruz, G. M.; Lynch, V. M.; Canary, J. W.; Anslyn, E.V. J. Am. Chem.
Soc., 2011, 133, 13746-13752.
P47: Chirality Sensing with Metal-Ligand Supramolecular Architectures El. Badetti, Giulia Licini and C. Zonta Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, [email protected]
Abstract: Optical probes own generally a molecular fragment present in two enantiomeric forms which in
presence of an analite give rise to a preferential diasteroisomer able to furnish an optical readout.1
Recently we reported about a new molecular probe used for the reliable determination of the enantiomeric
excess of free amino acids.2 In this communication we will discuss the use of new metals and the
measurement of the induced circular dichroism of the resulting multicomponent assembly. The study
highlights the complex equilibria present in solution for the formation of the assembly and the specie
responsible of the CD signal (Figure 1).
Figure 1
1 N. Berova, L. Di Bari and G. Pescitelli, Chem. Soc. Rev., 2007, 36, 914-931. G. A. Hembury, V.V. Borovkov
and Y. Inoue, Chem. Rev. 2008, 108, 1-73. J.W. Canary, S. Mortezaei and J. Liang, Coord. Chem. Rev. 2010, 254, 2249-2266. D. Leung, S.O. Kang, E.V. Anslyn, Chem. Soc. Rev. 2012, 41, 448-479
2 F. A. Scaramuzzo, G. Licini and C. Zonta, Chem. Eur. J. 2013, 19, 16809–16813
size of the box
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P48: Solution studies to investigate derivatives of the {Pd84} wheel L. G. Christie, A. J. Surman, R. A. Scullion, D.-L. Long and L. Cronin WestCHEM School of Chemistry, University of Glasgow, University Avenue, Glasgow, G118QQ, United Kingdom. [email protected]; [email protected]
Abstract: Polyoxometalates (POMs) are a family of metal-oxygen clusters whose aesthetically pleasing framework topologies and diverse range of potential applications (e.g. catalysis and medicine) have attracted a great deal of attention over the last few decades.[1] Until recently, POMs were mostly limited to metals such as Mo, W, and V, but have now grown to include ‘unconventional’ metals such as Pt, Au, and Pd.1-3 The largest of these unconventional metal POMs is the {Pd84} macrocycle which has an overall diameter of 3nm.4 We are interested in creating variations of this macrocycle by swapping the inner and outer acetate ligands for different functional groups. Herein, we describe the discovery of two novel palladium based macrocycles. The first is a {Pd72} wheel molecule, identified crystallographically, made using propionate ligands in place of the conventional acetate. We present solution studies carried out using size exclusion high performance liquid chromatography (SE-HPLC) which reveal a structural analogue of the existing {Pd84} wheel, made using glycolate ligands. ESI-ion mobility mass spectra were collected, showing the CCSHe of the glycolate macrocycle to be comparable to that of conventional {Pd84}, and the propionate macrocycle CCSHe to be smaller than conventional {Pd84}. This work demonstrates the potential to vary the size of palladium macrocycles using ligand design.
Figure 1. The {Pd84} wheel with its minimal {Pd6} building block
References
1. M. T. Pope and A. Müller, Agnew. Chem. Int. Ed. Engl., 1991, 30, 34-48. 2. N. V. Izarova, N. Vankova, T. Heine, R. N. Biboum, B. Keita, L. Nadjo and U. Kortz, Angew. Chem. Int.
Ed., 2010, 49, 1886-1889.
3. E. V. Chubarova, M. H. Dickman, B. Keita, L. Nadjo, F. Miserque, M. Misfud, I. W. C. E. Arends, and U. Kortz, Angew. Chem. Int. Ed., 2008, 47, 9542-9546.
4. R. A. Scullion, A. J. Surman, F. Xu, J. S. Mathieson, D.-L Long, F. Haso, T. Liu and L. Cronin, Angew. Chem. Int. Ed, 2014, 126, 10196-10201.
P49: Synthesis and Characterisation of Catalysts for the Degradation of Organophosphorus Contaminants Yaroslav Kalinovskyy, Barry A. Blight, Marcus J. Main, Nick J. Cooper University of Kent, Ingram Building, Canterbury, Kent, CT2 7NH [email protected]
Abstract: Chemical warfare agents (CWAs) are a group of organophosphorus compounds which inhibit the enzyme acetylcholinesterase. CWAs disrupt the normal functioning of the nervous system and a lethal dose can result in respiratory failure and death. As CWAs are so toxic, we use simulant molecules to closely mimic their reactivity to enable us to screen their degradation using a range of catalysts. The goal is to develop a catalyst, which is stable amongst CWA degradation products (HF and HCl) and catalytic at low concentration, i.e 1% by weight relative to the substrate. The catalyst should facilitate a degradation process which relies entirely on atmospheric O2 and H2O for oxidation and hydrolysis. We report a number of heterogeneous catalysts such as Zirconium based metal organic frameworks1 (MOFs) and nanoporous cerium oxide capable of catalytic hydrolytic and oxidative degradation of CWA simulants. We also report some potential homogeneous hydrolysis catalysts consisting of Cu2+ and Zn2+ metal chelate complexes3, 4
Figure 1: Crystal Structure of DUT-52 Zirconium MOF2
1. Moon, Y. Liu, J. T. Hupp and O. K. Farha, Angewandte Chemie International Edition, 2015, 54, 6795 –6799 2. V. Bon, I. Senkovska, M. S. Weiss and S. Kaskel, CrystEngComm, 2013, 15, 9572-9577 3. H. Gao, Z. Ke, N. J. DeYonker, J. Wang, H. Xu, Z. Mao, D. L. Phillips and C. Zhao, J. Am. Chem. Soc., 2011, 133,
2904-2915 4. L. Tjioe, T. Joshi, C. M. Forsyth, B. Moubaraki, K. S. Murray, J. Brugger, B. Graham and L. Spiccia, Inorg.
Chem., 2011, 51, 939-953
P50: Nerve Agent Simulants Binding in Self-Assembled Cubic Coordination Cage M8L12 Chris G. P. Taylor & Michael D. Ward. University of Sheffield, Dainton Building, Brook Hill, Sheffield, S3 7HF [email protected]
Abstract: An increasing number of examples of self-assembled metal coordination cages have the ability to
bind guests within an internal cavity. This ability to bind guests allows for a range of exciting applications
such as drug delivery or even the control of a reaction. These Host-Guest interactions are highly dependent
on solvent effects and have been quantified for some guest series using two isostructural cages.1
G-series nerve agents, such as Sarin, are colorless, odorless and deadly. A series of nerve agent simulants
have been investigated and bound inside two isostructural cages. Binding constants have been determined
in both water and acetonitrile. Single crystal x-ray structures have been solved for DMMP in both
isostructural cages while DEMP has been solved in the water soluble cage.
Figures/Tables
Figure 1: Single crystal x-ray structures; (left) Water soluble cage with DEMP; (middle) Water soluble cage with
DMMP; (right) Acetonitrile soluble cage with DMMP.
Figure 2: (left) Structure of two G-series nerve agents; (right) Table of simulants guests with the volume and binding
constants in acetonitrile and water.
References
[1]. S. Turega, M. Whitehead, B. R. Hall, A. J. H. M. Meijer, C. A. Hunter, and M. D. Ward, Inorg. Chem., 2013, 52,
1122–32
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P51: Structural studies of a series of benzene 1,3,5 tricarboxamide derivatives Amy D. Lynes, Chris S. Hawes, Thorfinnur Gunnlaugsson School of Chemistry and Trinity Biomedical Sciences Institute, Trinity College Dublin. [email protected]
Abstract: Since their first synthesis 100 years ago by Curtius, benzene-1,3,5-tricarboxamides (BTA) have
become an important area of research, particularly in the area of supramolecular self-assembly. Owing to
their relatively simple structure and the wide range of derivatives available BTAs have an array of
applications, ranging from nanotechnology to biomedical applications.1 BTAs self-assemble into columnar
structures due to the hydrogen bonding between neighbouring amide groups.2 We have investigated the
effect of chain length and terminal group on the gelation and crystallisation properties of BTA derivatives
containing alkyl esters or carboxylic acids. The metal coordination properties of these compounds were also
exploited to generate a series of hybrid metallogels.
1. S. Cantekin, T. F. A. de Greef and A. R. A. Palmans, Chem. Soc. Rev., 2012, 41, 6125-6137. 2. O. Kotova, R. Daly, C. M. G. dos Santos, M. Boese, P. E. Kruger, J. J. Boland and T. Gunnlaugsson, Angew.
Chem. Int. Ed., 2012, 51, 7208-7212.
P52: Self-Assembly Studies of Tripodal Ligands: Towards Coordination Polymers and Luminescent Materials Savyasachi A. J., a Oxana Kotova, a David Caffrey,a Shaun Mills,b John J. Boland* b & Thorfinnur Gunnlaugsson*a a School of Chemistry and Trinity Biomedical Sciences Institute, Trinity College, Dublin, Ireland
b School of Chemistry and Centre for Research on Adaptive Nanostructures and Nanodevices, Trinity College, Dublin,
Ireland [email protected], [email protected].
Abstract: Self-assembly of organic molecules into well-defined organized structures has attracted
considerable research interest towards the development of new materials and their applications in diverse
fields such as molecular electronics, light-energy conversion, catalysis, soft materials and drug delivery
systems.1-4
We have shown the formation of supramolecular coordination polymers based on chiral terpyridine
tripodal C3-symmetrical ligands (L) and europium ions (Eu(III)). The synthesis of the R and S enantiomeric
pair was carried out in 5 steps with high yield. The complexation process between Eu(III) and ligands in both
lower (c = 5 × 10-6 M) and higher (c = 1 × 10-5 M) concentrations were observed through
spectrophotometric titrations conducted in MeOH. The binding model of stepwise addition of metal was
obtained by fitting the titration changes using nonlinear regression analysis program SPECFIT. Of these, the
changes in the absorption spectra gave excellent fits and the binding constants obtained for the 1:1, 2:1,
and 3:1 (M:L) species were similar for both enantiomers with logβ1:1 = 8.49 ± 0.16, logβ2:1 = 15.6 ± 0.17 and
logβ3:1 = 20.6 ± 0.19 for R ligand (Figure 1A). At the same time the binding constants for 1:1 and 3:2 species
were logβ1:1 = 6.31 ± 0.39, logβ3:2 = 26.0 ± 0.39 (Figure 1B).
Schematic representation of the formation of coordination polymers at concentration of CL = 1 × 10-5 M in MeOH. And solid state
emission properties and surface morphology of Eu-cyclene trimer complex.
1 T. Aida, E. W. Meijer and S. I. Stupp, Science., 2012, 335, 813-817. 2 J. D. Badjić, V. Balzani, A. Credi, S. Silvi and J. F. Stoddart, Science., 2004, 303, 1845-1849. 3 J.-C. G.Bunzli and C. Piguet, Chem. Soc. Rev., 2005, 34, 1048-1077. 4 O. Kotova, R. Daly, C. M. G. dos Santos, M. Boese, P. E. Kruger, J. J. Boland and T. Gunnlaugsson, Angew.
Chem. Int. Ed., 2012, 51, 7208-7212.
P53: Synthesis of a Fluorescent Zinc Complex for the Detection of Adenosine Triphosphate in Water Stephen J. Butler
Loughborough University, Department of Chemistry, Loughborough, LE11 3TU, UK
e-mail: [email protected]
Abstract: Adenosine triphosphate (ATP) is arguably one of the most important anions in living systems; it
serves as the chemical energy source for most biological functions and plays key roles in extracellular
signaling and DNA replication. The creation of synthetic probes that can signal the presence of ATP
reversibly and selectively could be used to quantify the energy supplied by ATP in different cellular
compartments. However, most reported ATP-selective probes are limited in utility, either because they
cannot effectively discriminate between polyphosphate anions or the detection range of the probe is too
low and does not match the levels of ATP present in cells (1–5 mM). Here, a fluorescent zinc complex
(Zn.L1) is presented, capable of the ratiometric detection of ATP in water in the presence of several
competing anions such as ADP, phosphate and bicarbonate.1 The probe was utilized to monitor the
apyrase-catalysed hydrolysis of ATP in real-time, in a medium that mimics extracellular fluid.2
Figure 1. Proposed binding mode of the ternary complex of Zn.L1 with ATP 1 S. J. Butler, Chem. Eur. J., 2014, 20, 15768-15774 2 S. J. Butler, B. K. McMahon, R. Pal, J. W. Walton and D. Parker, Chem. Eur. J., 2013, 19, 9511–9517.
Fig. 2. Synthesized compound(s) where R is the hydrophobic group which will drive the self-assembly and the amine is the positively charged binding site.
Fig. 1. Self-assembly enables high-affinity multivalent binding.
P54: Structure-Activity Relationships and Polyanion Selectivity in Self-Assembled Multivalent (SAMul) Nanostructures for Heparin Binding. Buthaina Albanyan and David K. Smith Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK [email protected]
Heparin binders are of importance due to their removal of this anti-coagulant from the body after major
surgeries.1 This work involves synthesizing a biocompatible nanostructured heparin binders by building a
self-assembling supramolecule to enhance multivalent binding (Fig. 1). These compounds consist of an
amine as the positively charged binding site and natural occurring fatty acid as the hydrophobic focal point
(R) to drive the assembly (Fig. 2). In order to determine whether the synthesized compounds have self-
assembled (form micelles) we measured their critical aggregation concentrations (CACs) by carrying out a
Nile Red assay.2 The heparin binding ability of these compounds in buffer and human Serum (100%) using a
displacement assay with a sensor dye (Mallard Blue)3 was monitored. In addition, we tested the
compounds binding abilities to DNA using an ethidium bromide displacement assay4 in order to determine
whether the same factors control binding to all polyanions. The results of our structure-activity relationship
study showed the effect of the alkene density in the hydrophobic tail on binding abilities. In addition,
modifying ligands has a notable effects on self-assembly and binding affinities. Interestingly, comparison
between DNA and heparin shows that not all polyanions are the same in terms of their binding preferences.
1. S. M. Bromfield, E. Wilde and D. K. Smith, Chem. Soc. Rev., 2013, 42, 9184-9195. 2. A. C. Rodrigo, A. Barnard, J. Cooper, and D. K. Smith, Angew. Chem. Int. Ed., 2011, 50, 4675 –4679. 3. S. M. Bromfield, P. Posocco, M. Fermeglia, S. Pricl, J. R. Lopez and D. K. Smith, Chem. Commun., 2013, 49,
4830-4832. 4. H. Gershon, R. Ghirlando, S. B. Guttman and A. Minsky, Biochemistry, 1993, 32, 7143-7151.
P55: Crystallization in Microemulsions Stefanie Freitag-Pohl, J.W. Steed, S.J. Cooper Department of Chemistry, Durham University, South Road, Durham DH1 3LE [email protected]
Abstract: We investigate the crystallization of drug compounds with the help of microemulsion methods.1 Our model
system is the analgesic drug mefenamic acid (MA) which has been known to exist in two polymorphic forms
for a long time.2 Previous work from this lab showed that it is possible to crystallize mefenamic acid from
DMF microemulsions in the thermodynamic stable crystal form, I, whereas crystallization in bulk DMF
always gave metastable form II.3 Here, we investigate methods to enable nanocrystals within
microemulsion droplets to grow to macroscopic crystals more rapidly. One way to allow the initial
nanocrystals to grow readily is via seeding supersaturated MA solutions in different solvents with
microemulsions containing the nanocrystals; another is the swelling of the nanocrystal containing
microemulsion droplets with MA solutions. The swelling of MA/DMF microemulsions with different
MA/solvent solutions introduces a technique of manipulating the droplet solvent content. The method of
microemulsion crystallization could be a valuable tool in the search for new drug compound crystal forms.
1 C.E. Nicholson, C. Chen, B. Mendis and S.J. Cooper, Cryst. Growth Des., 2011, 11, 363-366. 2 A.J. Aguiar and J.E. Zelmer, J. Pharm. Sci., 1969, 58, 983-987. 3 C.E. Nicholson and S.J. Cooper, Crystals, 2011, 1, 195-205.
the size of the
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P56: Development of Modified Ferrocenes DNA Probes for Electrochemical SNP Sensing H. V. Roberts, J. Carr-Smith, J-L. H. A. Duprey, V-H. Nguyen, S. L. Horswell and J. H. R. Tucker. University of Birmingham, School of Chemistry, Edgbaston, Birmingham, B15 2TT [email protected]
Ferrocene is used regularly as a redox reporter within DNA as it is easily manufactured
within the lab, functionalisable, stable and has well defined electrochemical behaviour
making it an excellent candidate for DNA sensing. Here we present a modified ferrocene
unit for use within a DNA-based surface bound electrochemical probe.
Ferrocene modified with a base on each cyclopentadienyl ring has been synthesised and
substituted for two of the sugar units in the DNA backbone using automated DNA
synthesis. This allows for the so-called FcNA unit to be placed as close as possible to the
site of a DNA base variation (called a single nucleotide polymorphism or SNP) within a target strand upon
duplex formation. This approach could give a sensitive, portable, reusable and rapid SNP detector leading
to quicker medical diagnosis and treatment.1
SAM formation of a FcNA-DNA conjugate on a gold electrode (see left)
gives reproducible redox behaviour in its single stranded form and
upon hybridisation with its target strand. Investigations using Square
Wave Voltammetry (SWV) suggest an unusual increase in current on
binding to a complementary DNA strand due to the effect of increased
molecular rigidity.
The probe shows good chemical and electrochemical stability, losing only 2% current signal over 150 scans
and no apparent degradation on storage in a NaCl solution over 72 hours, despite the literature reporting
that ferrocene derivatives containing tags at the ends of strands are generally unstable in this medium.2
1 V. Nguyen, H.; Zhao, Z.; Sallustrau, A.; Horswell, S. L.; Male, L.; Mulas, A.; Tucker, J. H. R. Chem. Commun. 2012, 48, 12165–12167.
2 White, R. J.; Plaxco, K. W. Anal. Chem. 2009, 82, 73–76.
P57: Knots in self-assembled peptides and in oscillating chemical reactions A. Cincotti, E. H. C. Bromley, J. W. Steed Durham University, Stockton Road, Durham, DH1 3LE, UK, [email protected]
Abstract: Knotted molecules have always represented a big synthetic challenge for chemists as a
consequence of their highly organized structures. Such structures require significant synthetic control over
the conformation of the molecules. The Scientific Properties of Complex Knots (SPOCK) project is an
interdisciplinary collaboration between Durham University and the University of Bristol. It aims to explore a
wide variety of knots from different perspectives, including areas of mathematics, physics and
anthropology. From the chemistry aspect, the research efforts are concentrated in two main areas.
The first project is focused on the development
of a large, self-assembling biomolecular system
composed of two complementary peptides.
These peptides can form a parallel heterodimeric
coiled-coil. A previous study on this system
showed that two of these α-helical peptides,
when joined by flexible linkers of variable
lengths, can produce a range of different
assemblies depending on the number of amino
acids between the two helices.1 Particularly
interesting for us is the case of the formation of trimeric and tetrameric nanoscale macrocycles. The
knotting of this biomolecular self-assembly will be attempted by the addition of a cysteine residue at each
end of the monomer. This will allow the formation of intermolecular disulphide bonds, which will hopefully
lead to a closed knotted structure (Fig. 1).
The second project aims to obtain knotted shapes of chemical concentration
waves in a photosensitive Belousov-Zhabotinsky reaction medium. The BZ
reaction is a well-known example of non-equilibrium oscillatory dynamics, due to
a rather complicated mechanism.2 The oscillations between two oxidation states
of a Ruthenium catalyst immobilized in a silica gel matrix make it possible to
propagate visible waves (Fig. 2), and to control them with light by the
photosensitivity of the catalyst. Our purpose is to induce three-dimensional
knotted shapes in the wave’s pacemaker, by using specific light patterns.
1 A. L. Boyle, E. H. C. Bromley, G. J. Bartlett, R. B. Sessions, T. H. Sharp, C. L. Williams, P. M. G. Curmi, N. R. Forde, H. Linke and D. N. Woolfson, J. Am. Chem. Soc., 2012, 134, 15457–15467.
2 R. Toth and A. Taylor, Prog. React. Kinet. …, 2006, 31, 59–115.
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Fig. 1: Knotted tetrameric and trimeric
self-assemblies should form
a Solomon knot and a trefoil knot respectively
Fig. 2: Spiral waves in a photosensitive BZ reaction
P58: Photoinduced Energy- and Electron-Transfer Host/Guest Assemblies Based on Water Soluble Coordination Cage J. R. Piper and M. D. Ward Department of Chemistry, University of Sheffield, Brook Hill, S3 7HF [email protected]
A water-soluble Cd8L12 cubic coordination cage is fluorescent because of an array of naphthyl groups which
surround the central cavity. In water hydrophobic organic guests can bind strongly in the cavity if they are a
good shape/size match. 1
Binding of guest molecules results in quenching of the cage’s fluorescence; Guests with suitable properties
provide deactivation of the naphthyl excited state by either photoinduced energy- or electron-transfer.
Examples of guests that quench cage fluorescence by either mechanism are presented: guests with suitable
absorption energies proceed via a cage to guest energy-transfer pathway. Guest molecules with good
electron accepting properties deactivate the naphthyl excited state by means of a naphthalene to guest
electron transfer resulting in a charge separated state.
1 M. Whitehead, S. Turega, A. Stephenson, C. A. Hunter and M. D. Ward, Chem. Sci., 2013, 4, 2744-2751
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300 350 400 450 500 550 600
Flu
ore
sce
nce
In
ten
sity (
a.u
.)
Wavelength (nm)
Fig. 1 Structure of the [M8(Lw
)12](BF4)16
cage. 4 of the 12 bridging ligands are shown. 1
Fig. 2 Fluorescence titration graph of
[Cd8(Lw
)12]16+
fluorescence with 7-amino-4-
nitrobenzofurazan. Showing quenching of
[Cd8(Lw
)12]16+
emission and increasing sensitised
emission of the guest; Excitation at 290 nm in water.
P59: Aligning Perylene Bisimides Films for Enhanced Photoconductive Properties E. R. Draper, M. Wallace, O. O. Mykhaylyk, A. J. Cowan, D. J. Adams. Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD, U. K.. [email protected]
We have shown that a series of amino acid functionalised perylene bisimides (PBI) form aggregates in
solution that exhibit photoconductive behaviour upon irradiation exclusively with UV light.1 PBIs show
promise for use as n-type materials in organic electronics such as photovoltaic devices. Their suitability as
n-type materials in such devices stems from their absorption, emission and conductivity properties. Their
conductivity arises from the formation of a radical anion upon shining light on the sample. The PBI
molecules form fibre-like aggregates, these are formed by self-assembled π-stacking of the molecules in
aqueous solution at high pH due to their hydrophobicity. By aligning these aggregates in solution before
drying into a thin film, the pathway of the electron is shorter. A shorter path length shows a greater
conductivity. We show by drying PBI solutions in the presence of a magnetic field, we are able to form well
defined aligned structures compared to when allowed to dry in air. We also are able to align solutions and
gels using shear to give reproducibly aligned films (Fig. 1a and b). These films show great directional
dependence with larger currents along the alignment of the fibres than against the alignment of the fibres.
This ability to reproducibly align the structures is essential for their use in application such as p-n
heterojunctions.
Figure 3. Opitical microscope images under cross-polarised light of (a) solution under shear and (b) a shear aligned dried film.
1 E. R. Draper, J. J. Walsh, T. O. McDonald, M. A. Zwijnenburg, P. J. Cameron, A. J. Cowan and D. J. Adams, J. Mat. Chem. C, 2014, 2, 5570-5575.
P60: Synthesis and Characterisation of a Novel BODIPY-Dimer Compound Razan Alshgari, E. Stephen Davies, Victoria J. Richards, William Lewis and Neil R. Champness School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK [email protected]
Abstract: The BODIPY class (4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene) is considered one of the
most versatile fluorescent reagents and has become increasingly popular over the last two decades. These
dyes have a number of unique characteristics that make them of great interest including insensitivity to the
polarity and pH of their environment, excellent stability, intense absorption profile, high fluorescence yield
and good solubility.
The major aim of this project is to focus on the synthesis of a novel BODIPY-dimer compound and to study
the properties and interplay between the two BODIPY moieties. The preparation of this compound requires
reaction of a BF2-dipyrromethane precursor with the bridging catechol unit and the structure of the product
was confirmed by single crystal X-ray diffraction studies and standard spectroscopic and spectrometric
techniques (Figure 1). The single crystal structure confirms an orthogonal relationship between the dipyrrin
and catechol moieties.
Figure 1: Single crystal structure of the BODIPY-dimer.
The redox behaviour of the BODIPY-dimer was studied using cyclic voltammetrey (CV) and UV/Vis
spectroelectrochemistry measurements. These experiments indicate two chemically reversible oxidation
processes at -0.10 V and +0.68 V and one chemically irreversible reduction process at -1.20 V. Studies
confirm that whereas oxidation is based upon the catechol fragment, reduction is based on the dipyrrin
units consistent with previous studies of catechol substituted BODIPY systems.1
1 V.J. Richards, A.L. Gower, J.E.H.B. Smith, E.S. Davies, D. Lahaye, A.G. Slater (neé Phillips), W. Lewis, A.J. Blake, N.R. Champness and D.L. Kays, Chem. Commun., 2012, 48, 1751–1753.
P61: Multinuclear NMR to Understand Peptide Surface Chemistry and Gelation Matthew Wallace, Jonathan A. Iggo and Dave J. Adams Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK. [email protected]
Supramolecular hydrogels are formed via the self-assembly in solution of low molecular weight gelators
and have a wide range of potential applications as diverse as cell culturing and catalysis. A number of well-
established analytical techniques exist for the study of such hydrogels at the molecular level, the focus
being on how the gelator molecules are packed together in the self-assembled gel fibres.1 Hydrogels,
however, are hierarchical systems with the primary gel fibres further associating with one another to form
larger-scale structures that constitute the bulk macroscopic gels. Techniques for probing the surface
chemistry of the gel fibres are thus required in order to build a better understanding of how the hydrogels
are formed as well as their suitability for different applications; however, such techniques remain relatively
underdeveloped. To this end, we are developing a range of techniques based on solution-state NMR
spectroscopy to probe the surface charge, hydrophobicity and ion binding dynamics of hydrogel fibres. The
fibres themselves are invisible by conventional solution-state NMR, but much valuable information can be
obtained by studying instead their selective interaction with probe molecules dissolved in the bulk solution
of the gel. For example, by measuring the relative residual quadrupolar couplings, (), of NH4+ and
isopropanol-d8 as the pH of the bulk solution is decreased, we are able to follow the loss of charge from the
gel fibres which leads to a stiffening and contraction of the bulk gel.2 In other systems, we are also able to
observe the displacement of Na+ ions by Mg2+ or Ca2+ from a peptide fibre. We are developing chemical
shift imaging (CSI) techniques to follow the formation of hydrogels along chemical gradients, for example
pH or Mg2+ gradients, thus extending our techniques to the study of such inhomogeneous samples. Many
hydrogel systems, such as those triggered by the addition of metal salts,3 must be prepared via the
diffusion of the trigger substance throughout the solution of the gelator and thus their formation cannot be
followed by conventional one-dimensional NMR spectroscopy which requires homogeneous samples.
1 G. Yu, C. Yan and F. Huang, Chem. Soc. Rev., 2013, 42, 6697-6722. 2 M. Wallace, J. A. Iggo and D. J. Adams, Soft Matter, 2015, 11, 7739-7747. 3 L. Chen, G. Pont, K. Morris, G. Lotze, A. Squires, L. C. Serpell and D. J. Adams, Chem. Commun., 2011, 47,
12071-12073.
P62: Co-precipitation of SPIONs: how synthesis conditions affect particle properties, stem cell labelling, and MR contrast. Michael Barrow, Arthur Taylor, Jaime Garcia Carrion, Pranab Mandal, Harish Poptani, Patricia Murray, Matthew J. Rosseinsky, Dave J. Adams. University of Liverpool, Department of Chemistry, Liverpool [email protected]
Abstract: Superparamagnetic iron oxide nanoparticles particles (SPIONs) are widely used pre-clinically as
contrast agents for stem cell tracking using magnetic resonance imaging (MRI). The total mass of iron oxide
that can be internalised into cells without altering their viability or phenotype is an important criterion
towards the generation of contrast and SPIONs designed for efficient labelling of stem cells can allow an
increased sensitivity of detection.
We have synthesised a series of cationic SPIONs with very similar hydrodynamic diameters and surface
charges and report how subtle changes in the amount of polymer used in the co-precipitation synthesis can
affect both core size and overall polymer content, therefore modulating not only the magnetic properties
of the SPIONs but also their uptake into stem cells. SPIONs with the largest core size presented the highest
relaxivity and uptake into stem cells, significantly affecting the amount of contrast that can be generated.
We explore how cell confinement affects the relaxometric properties of SPIONs and how that can affect the
imaging of SPION labelled stem cells.
The physiochemical properties of SPIONs were characterised using DLS, zeta potential, UV-Vis, TGA, pXRD,
magnetic resonance and SQUID magnetometry. We also used magnetic separation to investigate how the
size and surface charge of SPIONs can change after exposure to cell culture medium.
P63: Identification and ultrafast investigation of the bright and dark excited states of the [Ru(phen)2(dppz)]2+ light switch and working towards transient absorption studies of a photoactive complex in cancer cells. Fergus E. Poynton, Sandra A. Bright, James P. Hall, Christine Schwarz, Paraic M. Keane,Susan J. Quinn, Igor V. Sazanovich, Ian Clark, Greg Greetham, Michael Towrie, David J. Cardin, Christine J. Cardin, D. Clive Williams, Thorfinnur Gunnlaugsson, John M. Kelly. School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, Dublin 2 Ireland [email protected]
Abstract: Self-assembly is an essential process in biology and underlies the mechanism of cellular
reproduction and transcription of the genetic code of DNA. Therefore studying the covalent and non-
covalent binding of small molecules to DNA and evaluation of their ability to interfere with or control such
processes represents an opportunity to elucidate new paradigms in cancer therapy.1 Transition metal
complexes based on dipyrido[3,2-a:2’3’-c]phenazine (dppz) have been extensively studied as probes for
DNA and as cytotoxic agents.2, 3 Herein we present picosecond time-resolved mid-IR (ps-TRIR) studies of
two such complexes, a luminescent DNA probe and a photo-cytotoxic agent,2, 4 in order to investigate the
interactions of these complexes with DNA (Figure 1) and when in a biological environment within cancer
cells.
Figure 1: X-ray molecular structure of [Ru(phen)2(dppz)]2+ and its picosecond time-resolved mid-IR spectrum in CD3CN, D2O and when bound to DNA. 1. J. Stubbe and J. W. Kozarich, Chem. Rev, 1987, 87, 1107-1136. 2. Y. Jenkins, A. E. Friedman, N. J. Turro and J. K. Barton, Biochemistry, 1992, 31, 10809-10816. 3. I. Ortmans, B. Elias, J. M. Kelly, C. Moucheron and A. Kirsch-DeMesmaeker, Dalton Trans., 2004, 668-676. 4. S. M. Cloonan, R. B. P. Elmes, M. Erby, S. A. Bright, F. E. Poynton, D. E. Nolan, S. J. Quinn, T. Gunnlaugsson and
D. C. Williams, J. Med. Chem., 2015, 58, 4494-4505.
psTRIRpsTRIR
Ru in D2O
Ru in CD3CN
Λ-Ru + DNAΔ-Ru + DNA
Wavenumber (cm-1)
ΔA
bs
1300 1400 1500 1600 1700
List of Delegates
Professor Dave Adams University of Liverpool
Dr Louis Adriaenssens University of Lincoln
Mr Andi Affandi Newcastle University
Mrs Buthaina Albanyan The University of York
Miss Anna Aletti Trinity College Dublin
Prof Dr Valeria Amendola Università di Pavia
Mr Savyasachi Aramballi Jayanth Trinity College Dublin
Mr David Ashworth University of Sheffield
Professor Jerry Atwood University of Missouri - Columbia
Mr David August The University of Edinburgh
Mr Ian Bailey Biopharma
Ms Barbora Balonova University of Kent
Dr Michael Barrow University of Liverpool
Dr Enrico Berardo Imperial College London
Ms Debora Bestetti Strem
Dr Sean Bew University of East Anglia
Miss Aisha Bismillah University of Durham
Dr Barry Blight University of Kent
Mr Michael Bracchi Newcastle University
Mr Samuel Bradberry Trinity College Dublin
Mr Carlo Bravin University of Padova
Mr Samuel Bunce University of Leeds
Mr Michael Burke University of Edinburgh
Mr Kenneth Burns Biotage
Dr Stephen Butler Loughborough University
Dr Joseph Byrne Trinity College Dublin
Mr Yusuf Cakmak University of Manchester
Dr Ana Campo Rodrigo University of York
Mr Luca Catalano Politecnico di Milano
Mr Ching Wan Chan University of York
Miss Lorna Christie University of Glasgow
Mr Antonio Cincotti Durham University
Dr Mandy Cook Alfa Aesar
Professor Andrew Cooper University of Liverpool
Miss Heather Coubrough University of Leeds
Dr Peter Cragg University of Brighton
Mr William Cullen University of Sheffield
Dr Scott Dalgarno Heriot-Watt University
Miss Hannah Dalton Trinity College Dublin
Dr Krishna Kumar Damodaran University of Iceland
Mr Adam Deacon Johnson Matthey
Dr Jesus del Barrio Lasheras Schlumberger Research
Miss Emily Draper University of Liverpool
Mr Vasilios Duros University of Glasgow
Dr Robert Edkins University of Oxford
Dr William Edwards University of St Andrews
Kerry Elgie Asynt
Dr Sundus erbas cakmak University of Manchester
Miss Sandra Estalayo Trinity College Dublin
Dr Nicholas Evans Lancaster University
Mr Francisco Fernandez Politecnico di Milano
Dr Nick Fletcher Lancaster University
Dr Jonathan Foster University of Sheffield
Rowan Frame Royal Society of Chemistry
Mr Andrew Frawley Durham University
Dr Katharina Fucke Durham University
Dr David Fulton Newcastle University
Mr Charles Gell Lancaster University
Mr Dermot Gillen Trinity College Dublin
Dr Chris Hawes Trinity College Dublin
Miss Isabel Hegarty Trinity College Dublin
Miss Sarah Hewitt University of Leeds
Mrs Sarah Higginbotham Wiley
Mr Patrick Higgs Newcastle University
Dr Kate Horner Durham University
Professor Mir Wais Hosseini University of Strasbourg
Professor Andrew Houlton Newcastle University
Mrs Zainab Jaafar University of Sheffield
Dr Kim Jelfs Imperial College London
Ms Naomi Johnson University of Glasgow
Mr Lee Jones Fluorochem
Mr Tim Jones Biotage
Miss Anne Kathrine Junker Department of Chemistry, University of Copenhagen
Mr Yaroslav Kalinovskyy University of Kent
Dr Euan Kay University of St Andrews
Dr Oxana Kotova Trinity College Dublin
Dr Luisa Lascialfari Politecnico di Milano
Dr Gareth Lloyd Heriot-Watt University
Dr Paul Lusby University of Edinburgh
Miss Amy Lynes Trinity College Dublin
Dr Clare Mahon University of Leeds
Mr Nicolas Marro University of St Andrews
Dr Andrew Marsh University of Warwick
Mr Eoin McCarney Trinity College Dublin
Dr Paul McGonigal Durham University
Mr Charlie McTernan University of Manchester
Dr Alexander Metherell University of Sheffield
Prof Dr Pierangelo Metrangolo Politecnico di Milano
Mrs Maya Asyikin Mohamad Arif Durham University
Mr Brian Montgomery Hichrom
Mr Edward Neal University of Southampton
Dr Robert Pal Durham University
Miss Kristina Paraschiv University of Leeds
Professor David Parker Durham University
Miss Gemma Parker Durham University
Mr Jerico Piper University of Sheffield
Mr Bjorn Poulsen Trinity College Dublin
Mr Fergus Poynton Trinity College Dublin
Mrs Holly Roberts University of Birmingham
Miss Mousumi Samanta IISER Kolkata
Professor Oren Scherman University of Cambridge
Dr Christopher Serpell University of Kent
Mr Sergey Shuvaev Durham University
Professor Jonathan Steed Durham University
Professor Agnieszka Szumna Institute of Orgnaic Chemistry Polish Academy of Sciences
Mr Chris Taylor University of Sheffield
Dr Baiyang Teng University of Liverpool
Dr Javier Torroba-Velez Johnson Matthey PLC
Professor James Tucker University of Birmingham
Mr David van Brussel University of St Andrews
Mr Matthew Wallace University of Liverpool
Mr Mark Walsh Buchi
Professor Mike Watkinson Queen Mary University of London
Dr Marcus Winter Rigaku Europe
Mr Martin Woolley Fluorochem
Mr Weimin Xuan University of Glasgow
Prof Dr Cristiano Zonta University of Padova
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