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Kari Rissanen talks with CrystEngComm

Kari Rissanen

Professor Kari Rissanen is an Academy Professor at the Academy of Finland, where he is currently on leave from the University of Jyväskylä. He was first elected as Associate Professor of Organic Chemistry at University of Joensuu after completing his PhD in chemistry at the University of Jyväskylä.

His main interests lie in the fields of supramolecular chemistry, nanochemistry and X-ray crystallography, with a particular focus on weak intermolecular interactions in solid state materials, solutions and gaseous phases. His group are currently working on new self-organising organic nanoreactors, utilising combinations of metal coordination or halogen bonding, and halogen-bonded and organic two- or three-dimensional frameworks.

Here he talks with CrystEngComm about his first crystal structure, and his many projects in the field of supramolecular chemistry.

Why did you want to become a scientist?

I have been always interested in natural sciences, especially chemistry, and at best scientific research can be like detective work.

What projects are you working on at the moment?

My research is primarily based around the following Academy of Finland funded projects:

• Self-assembly of nano-sized supramolecular assemblies
• Functional materials by metal-directed self-assembly
• Supramolecular complexes and networks – design, photocontrol and function
• Intramolecular charge transfer (ICT) based fluorescent probes for monitoring zinc(II) and anions in gold nanoparticles
• New water-soluble chemo-responsive luminescent materials
• Weak interactions as structural elements in self-assembling molecular systems

What do you think will be the next big breakthrough in your field?

The full utilization of the sub-component self-assembly principle (pioneered by Jonathan Nitschke, Cambridge, UK).

How do you think Crystal Engineering will develop in the next couple of years?

To the understanding and utilization of the hierarchical order of multiple and simultaneously active weak intermolecular interactions.

What is the most rewarding aspect of your work?

I really enjoy being able to help and tutor my students, postdocs and colleagues in resolving their difficult structural problems.

What is the secret to a successful research group?

Motivation and dedication to the research and persistence in overcoming encountered difficulties are all key to the success of a research group.

What achievement are you most proud of?

Winning two consecutive 5-year Academy Professorships – this is the most prestigious scientific research position in Finland.

What advice would you give to a young scientist?

Learn the basics well and keep an open and keen mind to everything new. Focus on your research and try to look it from a different perspective. In case of difficulty seek advice and help from more experienced colleagues and mentors.

What would you do if you weren’t a scientist?

Actually I have never though about this possibility, but maybe some kind of high school teacher?

What is your favourite space group and why?

R-3. Only 4 of my 850 published structures have this space group and in each case this space group has revealed a very interesting structure.

What was your first crystal structure?

Nickel salicylate. This was a product of my M.Sc thesis work which was published in Acta Chemica Scandinavica in 1987.

Read more about Kari’s work in the RSC articles below…

Self-ordering of metallogrid complexes via directed hydrogen-bonding
Artur R. Stefankiewicz, Guillaume Rogez, Jack Harrowfield, Alexandre N. Sobolev, Augustin Madalan, Juhani Huuskonen, Kari Rissanen and Jean-Marie Lehn
Dalton Transactions, 2012, Advance Article

Cooperativity of H-bonding and anion–π interaction in the binding of anions with neutral π-acceptors
Michael Giese, Markus Albrecht, Tim Krappitz, Marius Peters, Verena Gossen, Gerhard Raabe,  Arto Valkonen and Kari Rissanen
Chem. Commun., 2012, 48, 9983-9985

Kari Raatikainen and Kari Rissanen
CrystEngComm, 2011, 13, 6972-6977
(Previously highlighted on this blog!)
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Crystallography Centennial Celebrations

Crystallographers everywhere have lots of reasons to celebrate in the years 2012-2014 for the centennial of Laue and the Braggs’ discoveries. Already this year there have been conferences held to highlight Laue’s contributions, such as the Laue Day held during the 20th Annual Meeting of the German Crystallographic Society. There will be many events in 2012-2013 to celebrate the work of the Braggs’, including the Bragg Symposium being held during the AsCA 12/CRYSTAL28 meeting in Adelaide, Australia in December 2012, and exhibitions at the European Crystallographic Meeting 2013 in Warwick, UK. The IUCr recently announced that 2014 has now been officially designated ‘International Year of Crystallography‘ by the United Nations, and so we can be sure the celebrations will continue through to the next IUCr Congress in Montréal and beyond!

2014 is the International Year of Crystallography

Are you planning an exciting event to celebrate the wonderful discoveries of Laue and the Braggs’? Let us know in the comments box below!

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AsCA 12/CRYSTAL 28

The Asian Crystallographic Association (AsCA), Society of Crystallographers in Australia and New Zealand (SCANZ) and the Bragg Symposium are holding the AsCA 12/CRYSTAL 28 meeting in Adelaide between the 2nd-6th December 2012 to celebrate the important anniversary of the Braggs’ discoveries in X-ray diffraction.

The meeting features a range of sessions including non-ambient and in-situ diffraction studies, chemical crystallography, and dynamic aspects of molecular and solid state crystals. Plenaries from Prof. Xiao-Ming Chen (Sun Yat-Sen University, Guangzhou)  and talks from Prof. Evan Gray (Griffith University, Australia) and Prof. Jagadese Vittal (University of Singapore) have been announced. The Bragg Symposium will take place following the conference on the 6th December at the Elder Hall at the University of Adelaide, with invited speakers like Prof. Sir Colin Humphreys (University of Cambridge, UK) and Mrs Patience Thomas (younger daughter of Sir Laurence Bragg).

Early bird registration will close on the 1st September 2012, and abstract submission closes on 31st August 2012. Register now and don’t miss out!

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30th Spring Meeting of the British Crystallographic Association

I recently attended the 30th annual Spring meeting of the British Crystallographic Association at the University of Warwick from 16th-19th April 2012. The program was chaired by Kirsten Christensen (University of Oxford), and included a broad range of lectures from all areas of crystallography.

The Young Crystallographers Group satellite opened the meeting. This is an excellent forum for early stage researchers to present their work in a relaxed and friendly environment. There were 14 students talks in total, all of a very high standard, and two plenaries by Kenneth Shankland and Robin Owen. The Parkin Lecture was awarded to Lynne Thomas (University of Bath) for her outstanding work in outreach and crystallography. Jessica Bland from the Royal Society also came and spoke about the challenges and rewards of science communication, and encouraged everyone to get involved!

Young Crystallographers Group satellite speakers

Back row: Robin Owen, Claire Murray, Andrew Maloney, Ed Pyzer-Knapp, Karun Arachige. Middle row: Jessica Bland, Alexander Graham, Marco Llamas, Soshichiro Nagano, Thembaninkosi Gaulle, Alan Martin. Front row: Richard Martin, Ioana Sovago, Lynne Thomas, Callum Young, Karim Sutton. With thanks to Allan Pang for the photograph.

The main meeting opened on the second day with a biological group plenary by Laurence Pearl (University of Sussex) discussing his work on the structural biology of the DNA damage response. The subsequent sessions covered multidimensional materials and multidimensional approaches. A forum for opening dialogue between small molecule and macromolecular crystallographers proved to be very popular, with plenty of questions flying between the two communities. Throughout the day there was an art installation by Fevered Sleep called ‘Stilled’ in Warwick arts centre, which used pinhole cameras to capture images of dancers. This was originally commisioned by the Wellcome Trust in 2008, and was very well received at the conference. The evening poster session was very busy, and there was lots of exciting crystallography to be seen and discussed.

The third day of the conference started with a chemical plenary by Robin Taylor in honour of Frank Allen (CCDC), probing the redundancy of crystal structure data. Whilst larger, more complicated structures require a lot more work, the advances in computational chemistry mean it is possible to predict many low energy conformers for smaller organic materials. The morning sessions included awards for early stage scientists. Gareth Lloyd (University of Cambridge) received the CCG/CCDC prize for his work on supramolecular gels. Jon Wright (ESRF) received the physical crystallography prize for his work on the Verwey transition of magnetite. The final award was from the industrial group for the best student talk, and this was awarded to Andrew Maloney (a PhD student in the group of Simon Parsons), who discussed his work on modifying the PIXEL method to calculate intermolecular interaction energies for transition metal complexes. After two sessions on hydrogen bonding, the industrial plenary was given by Dan Shechtman who presented a lively and illuminating overview of his nobel prize winning work on quasi periodic crystals. See my recent interview with Dan here

Dan Shechtman pictured. With thanks to Allan Pang for the photograph.

The conference dinner included a ceili and the poster prizes. The CrystEngComm poster prize was awarded to Peter Galek (CCDC) for his poster on ‘H-Bonding landscapes for the assessment of polymorphs, co-crystals & hydrates’. Congratulations Peter!

CrystEngComm poster prize winner Peter Galek

The final day of the conference with the physical plenary by Branton Campbell (Brigham Young University) discussing his work on incommensurate structures using group theory enumeration. Sessions on phases transitions closed the conference. The next BCA Spring meeting will be held in Loughborough in 2014, and will be chaired by Lee Brammer (University of Sheffield).

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CPOSS meeting

A few weeks ago, I attended the 6th annual meeting of the “Control and Prediction of the Organic Solid State” (CPOSS) project in the Old Refectory of University College London. The meeting was themed ‘Crystals or not – where do we go from here?’. There were over 100 delegates in attendance, with both academic and industrial members present.

Sally Price (University College London) opened the morning session with an outline of the CPOSS project achievements to date. Tackling the over-prediction of polymorphs, she issued a caution when deciding that unobserved thermodynamically feasible structures cannot appear. The case of the carbamazepine form V polymorph clearly demonstrated this, as it could in fact be isolated by seeded sublimation! Alastair Florence (University of Strathclyde) followed, focusing on the complementary nature of experimental and computational methods to characterise racemic and enantiopure naproxen. The calculated crystal energy landscape, binary melting point phase diagram, solubility measurements and limited solid-state screening, were all consistent with the racemic Pbca and enantiopure P21 compounds being the only practically relevant solid phases of the free acid naproxen.

A slight diversion in theme by Simon Gaisford (University College London) revealed a novel method for identifying polymorphs by thermal methods rather than crystallographic techniques. Different polymorphs have different melting temperatures and heats of fusion. By varying the rate of heating, it was possible to isolate a metastable carbamazepine-nicatinamide cocrystal polymorph. The final talk of the session was by Matthew Hapgood (University College London) who discussed the intriguing case of tetrolic acid, where the lowest global minima of the crystal energy landscape are not the actual alpha or beta polymorphs. By combining solution simulations and nanocrystalline molecular cluster stability calculations, it was possible to extract the actual crystal structures from predictions of energy landscapes.

Speakers at CPOSS

From left to right: Professor Chick Wilson (University of Bath), Dr Philippe Fernandes (formerly University of Strathclyde), Dr Sharon Cooper (University of Durham), Professor Sally Price (UCL), Professor Jon Steed (University of Durham), Professor Derek Tocher (UCL), Dr Matthew Habgood (UCL), Dr Doris Braun (UCL), Professor Alastair Florence (University of Strathclyde). Photo courtesy of Louise Price.

Following lunch and a busy poster session, the afternoon session started with a presentation by Jon Steed (University of Durham) on crystallisation in anion-switchable supramolecular gels, with a particular focus on producing materials with switchable flow characteristics. Sharon Cooper (University of Durham) offered an interesting way to try to overcome kinetic control of metastable polymorphs (such as the infamous case of Ritonavir) through the use of microemulsions driven by thermodynamic control for polymorphic compounds like mefenamic acid and γ-glycine. Phillippe Fernandes provided a personal overview of his experience in solid-state chemistry, both from an academic and an industrial point of view.

Doris Braun (University College London) emphasized that contact with water cannot be avoided during the manufacturing process of pharmaceuticals. The already complex crystal structure predictions thus require the additional step of hydrate formation predication in order to more accurately predict polymorph formation, such as for 2,4-Dihydroxybenzoic acid and 2,5-Dihydroxybenzoic acid. The session was concluded by Chick Wilson (University of Bath) as a champion of the Directed Assembly of Extended Structures Network. He presented the activities and future plans of this network, which aims to foster collaborations in order to be able to design, engineer and control materials for applications in frontier manufacturing and other industries.

The meeting was enjoyed by all, and was an excellent overview of the current status of structure prediction, as well as highlighting challenges still facing solid-state chemists. Look out for my interview with Sally Price also on the blog!

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Interview with Sally Price

Sally PriceProfessor Sally Price works at University College London in the UK. Her group focuses on developing the accurate modelling of intermolecular and intramolecular forces, in order to predict which crystal structures of an organic molecule are thermodynamically feasible. These are contrasted with experimental searches for polymorphs in order to understand the factors which lead to polymorphism, in a multi-disciplinary project “Control and Prediction of the Organic Solid State” (CPOSS – 2012 meeting report to follow soon here on CrystEngComm blog!).

She is on the Crystal Growth and Design Advisory Editorial Board and was a member of the CrystEngComm Editorial Board when the journal was first launched. Here, she talks to CrystEngComm about her near miss as a tax inspector, and her fasincation with the theoretical and atomic level understanding of chemistry.

Why did you want to become a scientist?

I’ve always liked understanding how things fit together – I had a chemistry and a Meccano set as a child. The summer before I started my A-level course, I worked at ICI as a lab technician, and I can recall the reaction of my supervisor when I said I wanted to be a theoretical rather than experimental chemist. At that stage I had barely heard of quantum mechanics, and was only expressing a liking for theory as being able to quantify relationships between measureable properties and make predictions.

What projects are you working on at the moment?

How do we model the forces in flexible organic molecules? The organic solid state is a great challenge to our theories of modelling inter and intramolecular forces adequately.

What do you think will be the next big breakthrough in your field?

It would be a breakthrough if computational chemistry and molecular modelling actually lived up to the hype and expectations, but it should slowly become a reliable complement to experimental work. We still have a long way to go in developing crystallisation science to have a more reliable theory, let alone implement such a theory to predict which crystal structures will form under which conditions. The required breakthrough is probably in understanding nucleation and growth in more realistic systems.

How do you think crystal engineering will develop in the next couple of years?

I subscribe to the dream of being able to design the assembly of new materials with targeted properties, but with the caveat that this will probably be the optimal compromise between the huge range of different properties required. For example, for pharmaceuticals, the primary property is biological effectiveness, and crystal engineering should define the variability in solubility, dissolution rate, mechanical stability, and ability to be formulated into a good delivery system.

What is the most rewarding aspect of your work?

The sheer aesthetic pleasure when various experiments and calculations come together to give an atomic level understanding.

What is the secret to a successful research group?

The people and their commitment to really understanding their research problem. A group with a mutually supportive atmosphere, where everyone helps each other, and feels able to make and receive suggestions and constructive criticisms about each other’s work, will be able to build more effectively on the work in the field.

What achievement are you most proud of?

In science, my more confident predictions of new crystal structures being experimentally verified, such as carbamazepine form V.

What advice would you give to a young scientist?

Write and rewrite your work continually as you are going along. Draft your aims and introduction before you start, add method and results as you are going, stacking up material for the SI, and keep rewriting your arguments and conclusions. Writing it down ensures that you think more clearly and critically about what you are doing, than just talking about it.

What would you do if you weren’t a scientist?

When it looked as if the Research Council (SERC) would not be funding anyone in the round when my postdoc grant was ending, I started investigating becoming a tax inspector. However, the exchange rates fluctuated in the right direction, before I had to find out whether that second choice would have suited. I don’t think it would have provided such a varied and satisfying career.

What is your favourite space group and why?

P1 – easy to visualise

What was your first crystal structure?

I have never solved a crystal structure, let alone prepared a sample. I lack the manual dexterity for experimental work. However, the first crystal structure I studied in detail was chlorine, to show that the anisotropy in the atom-atom repulsion and electrostatics, arising from the lone pair density could account for this structure. It was my first application of the theory of intermolecular forces to modelling crystal structure.

Read more about Sally’s work in the RSC articles below…

Screening for cocrystals of succinic acid and 4-aminobenzoic acid
Nizar Issa , Sarah A. Barnett , Sharmarke Mohamed , Doris E. Braun , Royston C. B. Copley , Derek A. Tocher and Sarah L. Price
CrystEngComm, 2012, 14, 2454-2464
Part of the recent themed issue Crystal engineering and crystallography in the pharmaceutical industry

Hydrate formation of dihydroxybenzoic acidsWhich, if any, hydrates will crystallise? Predicting hydrate formation of two dihydroxybenzoic acids
Doris E. Braun, Panagiotis G. Karamertzanis and Sarah L. Price
Chem. Commun., 2011, 47, 5443-5445

A strategy for producing predicted polymorphs: catemeric carbamazepine form V
Jean-Baptiste Arlin , Louise S. Price , Sarah L. Price and Alastair J. Florence
Chem. Commun., 2011, 47, 7074-7076

Quantifying intermolecular interactions and their use in computational crystal structure prediction
Sarah (Sally) L. Price
CrystEngComm, 2004, 6, 344-353

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Rare Ag···H-B interactions in coordination polymers

Carbaborane C-H groups are acidic and so are able to form hydrogen bonding interactions as donors. This can be exploited in the use of carbaboranes as coordinating anions that can be involved in agostic interactions with diverse metal centres. Agostic and electrostatic interactions for Ag···H-B are very rare.

In this advance article, Luís Cunha-Silva and Michaele Hardie report the synthesis and structural characterisation of two silver alkanedinitrile networks with cobalt carbaborane anions that have an exciting mix of short-range Ag···H interactions and geometries.

The complexes exhibit Ag centres that are purely coordinated by Ag···H-B interactions, which are highly uncommon coordination motifs. Both Ag···(H-B)4 and Ag···(H-B)6 centres were identified, and the cobalt carbaborane anions behaved as ligands through a mix of these agostic and electrostatic interactions.

This Hot Article is free to access for 4 weeks. You can keep up to date with the latest news in crystal engineering by liking us on facebook, following us on twitter or signing up to our e-alert service!

Exploring Ag•••H−B interactions in coordination polymers: silver alkanedinitrile networks with cobalt carbaborane anions
Luís Cunha-Silva and Michaele Hardie
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE00003B

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Interview with Alessia Bacchi

Professor Alessia Bacchi completed her undergraduate and graduate studies at the University of Parma. After completing a two year post doc in the European Molecular Biology Lab in Hamburg, she returned to the University of Parma in October 1998. Since October 2001, Alessia has been Associate Professor in the Faculty of Science, investigating the supramolecular organization in crystals as a model for the description of multicomponent systems and for the realization of new materials with complex properties. She is on the European Crystallographic Association Executive Committee and is the past chair of the IUCr Commission on Structural Chemistry. Here, she talks to CrystEngComm to tell us about her hopes for understanding crystal nucleation; her fascination with molecular models; and her enthusiasm for educating young researchers and students.

Why did you want to become a scientist?

I wanted to capture the deepest reasons behind what I could see. I have always been fascinated by building models to explain things.

What projects are you working on at the moment?

We are designing molecular materials that can adapt their solid state organization to include and reversibly release small guests, by reacting to external stimuli. We also work on polymorphs – a fascinating world where the more you look at things, the more you see fine details and unexpected results.

What do you think will be the next big breakthrough in your field?

I believe that understanding the process of nucleation, the very first stages of the birth of a crystal, would be a real step forward for scientists who design and fabricate crystalline materials.

How do you think crystal engineering will develop in the next couple of years?

The field is already on the cusp of fabricating novel materials with applications in the field of nanosciences in general. Also, control of crystal forms is becoming affordable. In a nutshell: less space for serendipity, more emphasis on control.

What is the most rewarding aspect of your work?

I still get excited when a prediction comes true, or when at the end of a lot of hard work I finally see the reason behind a particular observation. The education of young researchers and students is also an extremely rewarding aspect of academic life.

What is the secret to a successful research group?

To know each other’s strengths and weaknesses, and to be able to compensate one’s faults with someone else’s skills.

What achievements are you most proud of?

From a professional point of view, I was very proud to be invited as a lecturer at the Erice School in 2007. Erice schools are a real richness for the soul. On the research side, I cite two cases where I felt very proud that my predictions came true…

Just after finishing my PhD I predicted that there should be conformational polymorphism for rifamycins (a well known family of antibiotics) because I had been able to formulate a model of molecular flexibility previously overlooked (published in Journal of Medicinal Chemistry and Journal of Computer-Aided Molecular Design). Then I planned an unconventional crystallization experiment and ‘eureka’ the predicted form was there! I still remember the joy when I first saw the structure (published in New Journal of Chemistry). More recently, I had the crazy idea to predict the strength of intermolecular interactions by measuring crystal shape, and it worked! (published in Angewandte Chemie International Edition).

What advice would you give to young scientists?

To be ambitious and passionate in their work, to be honest and kind with colleagues and young students. Being a good person is the most important thing.

What would you do if you weren’t a scientist?

I would have probably become a teacher, or a medical doctor (or an explorer, or an archeologist, or a detective, or a champion at the Olympic Games….!)

What is your favourite space group and why?

P212121, because the origin is not in an obvious place or at the intersection of anything.

What was your first crystal structure?

A ligand that I synthesized during my thesis: bis(2-Pyridyl)ketone (phenyl(semicarbazono)acetyl)hydrazone monohydrate (CSD refcode PEBMAK)

Read more about Alessia’s research in the CrystEngComm articles below…

Water vapour uptake and extrusion by a crystalline metallorganic solid based on half-sandwich Ru(II) building-blocksWater vapour uptake and extrusion by a crystalline metallorganic solid based on half-sandwich Ru(II) building-blocks
Alessia Bacchi, Giulia Cantoni, Michele R. Chierotti, Alberto Girlando, Roberto Gobetto, Giuseppe Lapadula, Paolo Pelagatti, Angelo Sironi and Matteo Zecchini
CrystEngComm, 2011, 13, 4365–4375

Effects of “changing the wheels” on the inclusion properties in metal–organic diolsEffects of “changing the wheels” on the inclusion properties in metal–organic diols
Alessia Bacchi, Mauro Carcelli, Tiziana Chiodo and Francesco Mezzadri
CrystEngComm, 2008, 10, 1916–1927

Unusual hydrogen bonded (OH)4 tetrahedral nests organize zinc(II) coordination complexes in a non covalent diamondoid network
Alessia Bacchi, Elsa Bosetti and Mauro Carcelli
CrystEngComm, 2007, 9, 313–318

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2012 Gordon Research Conference on Crystal Engineering

The 2012 Gordon Research Conference on Crystal Engineering will be held in the Waterville Valley Resort, New Hampshire, USA from 10–15th June 2012.

The conference is chaired by Robin D. Rogers  alongside CrystEngComm Associate Editor, Christer Aakeröy  and Mike Zaworotko who are vice chairing). Sessions will include Nucleation, Crystal Growth, and Solid State Reactivity; Polymorphism and Crystal Structure Prediction; and Catalysis in Porous Materials. Susan Bourne (University of Cape Town), Lee Cronin (University of Glasgow), Pierangelo Metrangolo (Politecnico di Milano)  and Gautam Desiraju (Indian Institute of Science) have been invited to speak. Read my recent interview with Professor Desiraju here

There will be a Crystal Engineering Gordon Research Seminar before the conference on 9–10th June, focusing on the design, synthesis, and applications of metal–organic materials and coordination polymers. These seminars are a forum for graduate students, post-docs, and other scientists with comparable levels of experience and education to present and exchange new ideas. The deadline for registration for this seminar is 12th May 2012.

The application deadline for the conference is 13th May 2012. CrystEngComm Deputy Editor, Fiona McKenzie, is planning to attend and would love to meet you there if you are too – please let her know.

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European Crystallographic Meeting Bergen 2012

ECM Bergen LogoThe 27th meeting of the European Crystallographic Association (ECM27) will take place in Bergen, Norway from 6–11th August 2012.

The program committee have organised a rich scientific program of microsymposia and keynote lectures, with invited talks by CrystEngComm Editorial Board member Mark Spackman (University of Western Australia), Neil Champness (University of Nottingham, UK), Paola Gilli (University of Ferrara, Italy), and 2011 Nobel Prize winner in Chemistry, Dan Shechtman (Technion, Israel Institute of Technology) – read my recent interview with Dan here.

Prizes to be awarded at ECM27 include the European Crystallographic Association (ECA) Max Perutz Prize and the Erwin Felix Lewy Bertaut Prize of the European Crystallographic and Neutron Scattering Association (ECA-ENSA). The nomination deadlines for these awards are the 28th February and 31st March 2012, respectively.

There are two satellite meetings preceeding the main meeting on ‘Methods of High-Pressure Single Crystal X-ray Diffraction’ and the ‘Workshop on the Diffraction Data Deposition’.

Registration for this meeting is open now

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