Archive for the ‘Editor’s choice’ Category

Read our Editors’ Collection: Bioapplications of MOFs

We are delighted to share with you our latest collection of recently published articles focusing on Bioapplications of MOFs, handpicked by Associate Editor, Professor Christian Doonan, The University of Adelaide, Australia.

All of these articles are free to access until March 31st, 2021 and we hope you enjoy reading them.

We are pleased to invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

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Selected articles:

Mechanochemical approaches towards the in situ confinement of 5-FU anti-cancer drug within MIL-100 (Fe) metal–organic framework
Barbara E. Souza and Jin-Chong Tan
CrystEngComm, 2020,22, 4526-4530

Fabrication of a dual-emitting RhB@Zn-1 composite as a recyclable luminescent sensor for sensitive detection of nitrofuran antibiotics
Qian-Qian Tu, Ling-Ling Ren, Ai-Ling Cheng and  En-Qing Gao
CrystEngComm, 2021,23, 629-637

Synthesis of fluorescent MOFs: live-cell imaging and sensing of a herbicide
Aurobinda Mohanty, Udai P. Singh, R. J. Butcher, Neeladrisingha Das and  Partha Roy
CrystEngComm, 2020,22, 4468-4477

Read the full collection here

Meet the Editor

Christian Doonan is Professor of chemistry at the University of Adelaide. He received his PhD at the University of Melbourne and carried out post-doctoral work with Professor Omar Yaghi at the University of California, Los Angeles. His research group focuses on the design and synthesis of Metal-organic Framework materials for application to biotechnology and catalysis.

Christian is a member of the international MOF commission and his research has been recognised through several awards including, an Australian Research Council Future Fellowship, a distinguished lectureship award from the Chemical Society of Japan and a Double Hundred Talent Professorship at Qingdao University.

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Read our Editors’ Collection: MOF based catalysts for water splitting and CO2 reduction

We are delighted to share with you our latest collection of recently published articles focusing on Metal Organic Framework based catalysts for water splitting and CO2 reduction, handpicked by Editorial Board Member Professor Tong-Bu Lu, Tianjin University of Technology, China.

All of these articles are free to access until December 31st, 2020 and we hope you enjoy reading them.

We are pleased to invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

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Selected articles:

Covalently anchoring cobalt phthalocyanine on zeolitic imidazolate frameworks for efficient carbon dioxide electroreduction
Zhongjie Yang, Xiaofei Zhang, Chang Long, Shuhao Yan, Yanan Shi, Jianyu Han, Jing Zhang, Pengfei An, Lin Chang and Zhiyong Tang
CrystEngComm, 2020, 22, 1619-1624.

Polymorphs of a copper coordination compound: interlinking active sites enhance the electrocatalytic activity of the coordination polymer compared to the coordination complex
Pandi Muthukumar, Mehboobali Pannipara, Abdullah G. Al-Sehemi, Dohyun Moon and Savarimuthu Philip Anthony
CrystEngComm, 2020, 22, 425-429.

Understanding metal–organic frameworks for photocatalytic solar fuel production
J. G. Santaclara, F. Kapteijn, J. Gascon and M. A. van der Veen
CrystEngComm, 2017, 19, 4118-4125.

Read the full collection here

Meet the Editor

Tong-Bu Lu was born in 1964. He graduated in Chemistry from Lanzhou University in 1993, and then moved to Sun Yat-Sen University as a Postdoc. joining the Faculty and then becoming Professor of Chemistry in 2000. He moved to Tianjing University of Technology in 2016. He worked as a postdoc. in F. Albert Cotton’s group at Texas A&M University in 1998 and 2002. His research interests focus on crystal engineering, including macrocyclic chemistry, MOFs and pharmaceutical polymorphs and co-crystals. He currently focuses on the study on homogeneous and heterogeneous catalysts for water splitting and CO2 reduction. He obtained the National Natural Science Foundation for Distinguished Youth Scholar award in 2006. He has over 200 scientific publications and an h-index of 43. He is currently a fellow of the Royal Society of Chemistry (FRSC), is on the Editorial Board of CrystEngComm, the Editorial Advisory Board of Current Green Chemistry and Current Pharmaceutical Design and is a co-editor of Acta Crystallographica Section C.

 

 

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Read Our Editor’s Collection: Zirconium based MOFs for catalysis

We are delighted to share with you our latest collection of recently published articles focusing on Zirconium based MOFs for catalysis, handpicked by Editorial Board Member Omar K. Farha, Northwestern University, USA.

These articles are free to access until September 30th, 2020 and we hope you enjoy reading them.

We are very pleased to invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

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Selected articles:

Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework
Julia G. Knapp, Xuan Zhang, Tatyana Elkin, Laura E. Wolfsberg, Sylvia L. Hanna, Florencia A. Son, Brian L. Scott and Omar K. Farha
CrystEngComm, 2020, 22, 2097-2102

Ferrocenecarboxylic acid: a functional modulator for UiO-66 synthesis and incorporation of Pd nanoparticles
Zheng Deng, Xinsheng Peng and Yu-Jia Zeng
CrystEngComm, 2019, 21, 1772-1779

Synthesis, characterization, and post-synthetic modification of a micro/mesoporous zirconium–tricarboxylate metal–organic framework: towards the addition of acid active sites
Carolina Ardila-Suárez, Ana M. Díaz-Lasprilla, Laura A. Díaz-Vaca, Perla B. Balbuena, Víctor G. Baldovino-Medrano and Gustavo E. Ramírez-Caballero
CrystEngComm, 2019, 21, 3014-3030

Read the full collection here

Meet the Editor

Omar K. Farha is an associate professor of chemistry at Northwestern University, Distinguished Adjunct Professor at King Abdulaziz University, president of NuMat Technologies, and Associate Editor for ACS Applied Materials & Interfaces. His research accomplishments have been recognized by several awards and honours including the Royal Society of Chemistry “Environment, Sustainability and Energy Division Early Career” Award; the American Chemical society “The Satinder Ahuja Award for Young Investigators in Separation Science; and an award established by the Department of Chemistry at Northwestern University in his honour: the Omar Farha Award for Research Leadership “awarded for stewardship, cooperation and leadership in the finest pursuit of research in chemistry” and given annually to an outstanding research scientist working in the department. His current research spans diverse areas of chemistry and materials science ranging from energy to defence related challenges. Specifically, his research focuses on the rational design of metal–organic frameworks (MOFs) and porous-organic polymers for sensing, catalysis, storage, separations and light harvesting. Professor Farha has more than 300 peer-reviewed publications, holds 13 patents, and has been named a “Highly Cited Researcher” by Thomson Reuters in 2014, 2015, 2016 and 2017.

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Read our Editors’ Collection: Computer Aided Solid Form Design

We are delighted to share with you our latest collection of recently published articles focusing on Computer Aided Solid Form Design, handpicked by Editorial Board Member Susan Reutzel-Edens, Eli Lilly and Company.

These articles are free to access until July 31st 2020 and we hope you enjoy reading them.

We invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

Submit your research now

Selected articles:

Naphthalene crystal shape prediction from molecular dynamics simulations
Zoran Bjelobrk, Pablo M. Piaggi, Thilo Weber, Tarak Karmakar, Marco Mazzotti and Michele Parrinello
CrystEngComm, 2019, 21, 3280-3288.
DOI: 10.1039/C9CE00380K

Crystal-energy landscapes of active pharmaceutical ingredients using composite approaches
Luc M. LeBlanc and Erin R. Johnson
CrystEngComm, 2019, 21, 5995-6009.
DOI: 10.1039/C9CE00895K

Cocrystal design by network-based link prediction
Jan-Joris Devogelaer, Sander J. T. Brugman, Hugo Meekes, Paul Tinnemans, Elias Vlieg and René de Gelder
CrystEngComm, 2019, 21, 6875-6885.
DOI: 10.1039/C9CE01110B

Read the full collection here

Meet the Editor

Susan Reutzel-Edens. Royal Society of Chemistry, CrystEngComm Editorial Board Member

Susan Reutzel-Edens is a senior research advisor in Small Molecule Design & Development at Eli Lilly and Company and adjunct professor at Purdue University. After earning her PhD at the University of Minnesota (1991) under the direction of the late Professor Margaret C. Etter, she joined Eli Lilly, where she founded the solid form design programme and for two decades led a team of cross-functional scientists charged with finding commercially-viable crystalline forms for small-molecule drug products. She has contributed to the development of more than 150 compounds, is a named inventor on 12 US patents, and has published over 50 papers and book chapters on key aspects of solid form development. Her research interests include crystal polymorphism, materials design and engineering, crystal nucleation and growth, structure-property relationships, crystal structure prediction and digital design of drug products. She was elected Fellow of the Royal Society of Chemistry in 2018, and currently serves on the CrystEngComm Editorial Board, as a topic editor for Crystal Growth and Design, and is a member of the Editorial Advisory Board of Journal of Pharmaceutical Sciences and the Scientific Advisory Board of the Cambridge Crystallographic Data Centre.

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Read our Editor’s Collection on Mechanochemistry by Elena Boldyreva

We are delighted to share with you our latest collection of recently published articles focusing on Mechanochemistry, handpicked by Editorial Board Member Elena Boldyreva.

These articles are free to access until April 13th 2020 and we hope you enjoy reading them.

We invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

Submit your research now

Selected articles:

Dynamic behaviour in nonporous hybrid metal–organic materials via mechanochemical and gas–solid reactions
Fang Guo, Hao-Cheng Wang, Antonino Famulari, Hai-Dong Lu and Javier Martí-Rujas
CrystEngComm, 2018, 20, 6721-6726. DOI: 10.1039/C8CE01287C

On the kinetics of solvate formation through mechanochemistry
Dritan Hasa, Mariana Pastore, Mihails Arhangelskis, Benjamin Gabriele, Aurora J. Cruz-Cabeza, Gabriela Schneider Rauber, Andrew D. Bond and William Jones
CrystEngComm, 2019, 21, 2097-2104. DOI: 10.1039/C8CE00871J

Cocrystal formation by ionic liquid-assisted grinding: case study with cocrystals of caffeine
Arijit Mukherjee, Robin D. Rogers and A. S. Myerson
CrystEngComm, 2018, 20, 3817-3821. DOI: 10.1039/C8CE00859K

Read the full collection here

Meet the Editor

Professor Elena Boldyreva, CrystEngComm Editorial Board MemberEditorial Board Member Professor Dr Elena Boldyreva is currently employed by Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences and is the Head of the Chair of Solid State Chemistry of the Novosibirsk State University. Elena Boldyreva is an Honorary Doctor of Sciences of the University of Edinburgh, a Corresponding Member of the Academy of Sciences and Arts of Slovenia and a Member of the Academia Europea. She was a Humboldt Fellow and has spent many research terms in Germany, UK, Italy, France. She served as a member of the Executive Committee of the IUCr in 2008–2014.

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Read our Editor’s Collection on Chromism in Frameworks by Susan Bourne

We are delighted to share with you our latest collection of recently published articles focusing on Chromism in Frameworks handpicked by Associate Editor Susan Bourne.

These articles are free to access until December 31st 2019 and we hope you enjoy reading them.

We invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

 

Submit your research now

 

Featured articles:

Two novel multichromic coordination polymers based on a new flexible viologen ligand exhibiting photocontrolled luminescence properties and sensitive detection for ammonia
Hai Yu Wang, Shuang Liu, Chen Fu and Hong Zhang
CrystEngComm, 2019, 21, 1635-1641 DOI: 10.1039/C8CE01948G

Solvatomorphism of Reichardt’s dye
Sarah J. Pike, Andrew D. Bond and Christopher A. Hunter
CrystEngComm, 2018, 20, 2912-2915 DOI: 10.1039/C8CE00480C

The thermo-responsive behavior in molecular crystals of naphthalene diimides and their 3D printed thermochromic composites
Madushani Dharmarwardana, Bhargav S. Arimilli, Michael A. Luzuriaga, Sunah Kwon, Hamilton Lee, Gayan A. Appuhamillage, Gregory T. McCandless, Ronald A. Smaldone and Jeremiah J. Gassensmith
CrystEngComm, 2018, 20, 6054-6060 DOI: 10.1039/C8CE00798E

 

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CrystEngComm Associate Editor Susan Bourne Royal Society of Chemistry

 

 

 

Meet the Editor

Associate Editor Susan Bourne is the Professor of Physical Chemistry at the University of Cape Town. Her PhD, obtained at the University of Cape Town, was a study of organic inclusion compounds undertaken under the supervision of Professor Luigi Nassimbeni. Her research interests include the application of physicochemical methods to inclusion compounds and crystal engineering of metal-organic materials, all with the aim of correlating solid-state structure with physical properties and reactivity. She has published over 120 papers and has supervised 20 postgraduate students. She is the chair of the Structural Chemistry Commission of the International Union of Crystallography, and is a Fellow of the University of Cape Town.

 

 

 

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Read our Editor’s Collection on Polymorphism in Molecular Crystals by Aurora Cruz-Cabeza

We are delighted to share with you our latest collection of recently published articles focusing on Polymorphism in Molecular Crystals, handpicked by Editorial Board Member Aurora Cruz-Cabeza. This collection is dedicated to the late Professor Joel Bernstein who endeavoured much of his work to the study of polymorphism and inspired many of us.

These articles are free to access until October 31st 2019 and we hope you enjoy reading them.

We invite you to submit your research to CrystEngComm and give your work the global visibility it deserves.

 

Submit your research now

Featured articles:

L-Malic acid crystallization: polymorphism, semi-spherulites, twisting, and polarity
Jingxiang Yang, Chunhua T. Hu, Alexander G. Shtukenberg, Qiuxiang Yin and Bart Kahr
CrystEngComm, 2018, 20, 1383-1389. DOI: 10.1039/C7CE02107K

Serendipitous isolation of a disappearing conformational polymorph of succinic acid challenges computational polymorph prediction
Paolo Lucaioli, Elisa Nauha, Ilaria Gimondi, Louise S. Price, Rui Guo, Luca Iuzzolino, Ishwar Singh, Matteo Salvalaglio, Sarah L. Price and Nicholas Blagden
CrystEngComm, 2018, 20, 3971-3977. DOI: 10.1039/C8CE00625C

Polymorphism of chlorpropamide on liquid-assisted mechanical treatment: choice of liquid and type of mechanical treatment matter
Nadia Bouvart, Roland-Marie Palix, Sergey G. Arkhipov, Ivan A. Tumanov, Adam A. L. Michalchuk and Elena V. Boldyreva
CrystEngComm, 2018, 20, 1797-1803, DOI: 10.1039/C7CE02221B

 

Read the full collection here

Dr Aurora Cruz-Cabeza, CrystEngComm Editorial Board Member, University of Manchester

 

Meet the Editor

 

Editorial Board Member Dr Aurora Cruz-Cabeza is a Senior Lecturer at the University of Manchester, School of Chemical Engineering and Analytical Sciences. She has established her own research group in solid state chemistry and crystallisation. Aurora has authored over 50 research articles and has given over 60 research talks around the world. Some of her best well-known work lies in the area of polymorphism in molecular crystals.

 

 

 

CrystEngComm

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CrystEngComm Editor’s choice

In this Editor’s choice post, Professor Nicola Pinna, a member of  the CrystEngComm Editorial Board, talks about his favourite articles published in the journal in recent months. Nicola has chosen the most interesting articles in the area of controlled growth of nanostructured materials.  

Faegheh Hoshyargar, Enrico Mugnaioli, Robert Branscheid, Ute Kolb, Martin Penthofer and Wolfgang Tremel 
CrystEngComm, 2014, DOI:  10.1039/C4CE00326H    

Mechanistic analyses of nanoscale transformations are not easily accessible, however this case reported by Hoshyargar and co-workers is an exception as the authors managed to follow the transformation of tungsten oxide nanostructures to WS2 hollow particles. The starting material was synthesized by my favourite approach: a simple, solvothermal treatment of a tungsten alkoxide in benzyl alcohol, with the well-defined tungsten oxide nanoplatelets being subsequently converted to WS2 by sulfidization at higher temperature. The growth mechanism was investigated by applying advanced electron microscopy techniques at different stages of the solid state reaction. The final product, the “hollow rectangular WS2 nanoboxes”, was shown to be formed by “a cascade” of topotactic and epitactic processes. What I found the most astonishing was the last step of the mechanism, involving the fusion of the layered WS2 sheets forming almost perfect rectangular boxes with 90° kinks (see figure below).

layered tungsten sulfide sheets


Unconventional upright layer orientation and considerable enhancement of proton–electron conductivity in Dion–Jacobson perovskite thin films
Tomohiko Nakajima, Kiyoshi Kobayashi, Kentaro Shinodaa and Tetsuo Tsuchiyaa
CrystEngComm, 2014, 16, 4113-4119

Single crystal substrates are generally needed for growth of single-crystalline and highly-oriented oxide thin films. However, such an approach cannot be used in industrial applications for which the growth of highly-oriented oxide thin films should take place on common substrates. In this article, Nakajima et al. show that by pulsed laser-assisted annealing of an oxide precursor thin film that is spin coated from a molecular precursor solution, single crystalline RbCa2Nb3O10 layered perovskite thin films can be obtained. The peculiarity of these films is that they show upright layer orientations (see figure below) which may allow for them to be used as membranes for fuel cells due to the potential for high proton conductivity in the interlayer sites. The unusual orientation of the films is possibly connected to oxygen deficiencies near the surface which as caused by the high laser power needed to obtain the upright layer orientation.

layered perovskite thin films


Layered titanosilicates for size- and pattern-controlled overgrowth of MFI zeolite
Stanislav Ferdov
CrystEngComm, 2014, DOI10.1039/C3CE42644K

There is a need for controlling the growth of zeolites on different substrates which can only be achieved by understanding of the heterostructural interconnections between the support and the zeolite material.  This is particularly relevant for industrial applications such as catalysis. In this work, Stanislav Ferdov reports that plate-like crystals of two titanium silicates can act as interesting substrates for the controlled growth of an MFI-type zeolite. The different arrangement of the SiO4 tetrahedra and TiO6 octahedra in the two chosen titanosilicates govern the overgrowth behaviour. In one case, the plate-like crystals of the titanosilicate (20–40 μm) are covered with a monolayer of regularly packed-zeolite crystals (see figure below left). In the second case, the support acts as a single-nucleation site and only isolated and larger crystals of MFI zeolite are observed (see figure below right). Although the possibility for controlling the overgrowth of zeolites has clearly been demonstrated, the opportunity for improvement is huge. It can only be successful, however, if combined with a molecular-scale understanding of the heterostructural interconnections between substrate and zeolite.

MFI zeolites on layered titanosilicates


Ligand dynamic effect on phase and morphology control of hexagonal NaYF4
Suli Wu, Ye Liu, Jie Changa and Shufen Zhang 
CrystEngComm, 2014, DOI10.1039/C4CE00109E

It is well accepted that the adsorption of stabilizing ligands at the surface of nuclei dramatically influences the growth habit of inorganic nanocrystals. The organic–inorganic interface present in these systems is the key to the synthesis of morphology controlled nanocrystals. Ligands can selectively adsorb onto particular facets hindering the growth in the direction perpendicular to that facet. However, the adhesion energy of the ligands should be adjusted to allow dynamic adsorption-desorption during nanoparticle growth, as demonstrated in the past for the synthesis of quantum dots. More importantly, it has also been demonstrated that, for the same functional group, the dynamic effect on the surface of quantum dot nanocrystals is significantly influenced by the ligand chain length. In this article, the authors investigate the effect of the alkyl chain length of carboxylic acid ligands on the growth of NaYF4 nanocrystals. The much more mobile hexanoic acid (HA) does not effectively passivate the {001} facets leading to rod-shape nanoparticles. With longer alkyl chains ligands, the growth along the c-axis is decreased (see figure below) and the morphology can be almost continuously tuned from rods to very thin disk-shaped crystals. The authors attribute such precise morphology control to the different ligand dynamic as, for longer alkyl chain ligands, the tendency of leaving the (001) crystal surfaces decreases leading to a lower growth on the [001] direction.

hexagonal NaYF4


Nicola PinnaNicola Pinna studied physical chemistry at the Université Pierre et Marie Curie (Paris). He received his Ph.D. in 2001 and in 2002 moved to the Fritz Haber Institute of the Max Planck Society (Berlin). In 2003, he joined the Max Planck Institute of Colloids and Interfaces (Potsdam) before moving to the Martin Luther University, Halle-Wittenberg, as an Assistant Professor of Inorganic Chemistry in 2005. From March 2006 to June 2012 he was researcher at the Department of Chemistry and CICECO of the University of Aveiro and from September 2009 to June 2012 he was also Assistant Professor at the school of chemical and biological engineering Seoul National University. In July 2012 he joined the Department of Chemistry of the Humboldt University in Berlin. His research activity is focused on the development of novel routes to nanostructured materials, their characterization, and the study of their physical properties.

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CrystEngComm Editor’s choice

In this Editor’s choice post, Professor Christer Aakeröy, Associate Editor for CrystEngComm, talks about his favourite articles published in the journal in recent months. Christer has chosen the most interesting articles in the area of molecular recognition crystal engineering.  


Deprotonation of resorcinarenes by mono- and diamine bases: Complexation and intermolecular interactions in the solid state
N. Kodiah Beyeh,   Arto Valkonen and  Kari Rissanen 
CrystEngComm, 2013, DOI: 10.1039/C3CE42291G    

Structural chemistry investigations of macrocyclic compounds such as calixarenes and resorcinarenes are frequently hampered due to problems with crystal growth, and it is quite rare that a successful structural study is supported and complemented by solution- and gas-phase data.  Rissanen and co-workers have produced a systematic and comprehensive exploration of several deprotonated alkyl-resorcinarenes which offers a broad perspective of the structural and chemical behavior of representatives of a ‘classic’ supramolecular system.  The single-crystal studies indicate that the deprotonated macrocycles act as effective hosts for the protonated amines in the solid state and the acid-base behavior in solution is monitored by NMR titrations.  The deprotonated resorcinarenes (monomer and dimer) were observed using EI mass spectrometry in negative ion mode while the 1:1 and 2:1 complexes with the protonated guests were observed in positive ion mode in the gas phase.    

c3ce42291g   

 

Can self-assembly of copper(II) picolinamide building blocks be controlled?
Marijana Đaković, Diogo Vila-Viçosa, Nuno A. G. Bandeira, Maria José Calhorda, Bojan Kozlevčar, Zvonko Jagličić and Zora Popović 
CrystEngComm, 2013, 15, 8074-8087   

In this paper, Đaković et al examine the structural role played by picolinamide ligands in the directed assembly of a series of Cu(II) based complexes.   The study is supported by an impressive range of experimental and theoretical tools, and offers a comprehensive analysis and evaluation of an important aspect of crystal engineering.    The authors have examined the precise role that different factors play in the assembly of each structural motif and the outcome is a much enhanced understanding of the templating effect of the metal ion as well as of the complementarity of non-covalent interactions.  Finally, the structural work is supported by careful magnetic measurements the results of which are subsequently properly interpreted and rationalized using DFT-based calculations.   

Copper complexes self-assembly   

 

Knowledge-based hydrogen bond prediction and the synthesis of salts and cocrystals of the anti-malarial drug pyrimethamine with various drug and GRAS molecules
Amit Delori, Peter T. A. Galek, Elna Pidcock, Mohit Patni and William Jones 
CrystEngComm, 2013,15, 2916-2928   

The ability to determine which primary intermolecular interactions are most likely to take place given the presence of certain functional groups is of key importance in crystal engineering.  In this study, the authors adopt a knowledge-based approach that takes full advantage of the unique structural information that is provided within the Cambridge Structural Database.  Through the use of hydrogen bond propensity calculations (HBPC), which perform a statistical analysis of the occurrence of specific hydrogen bonds among structures of relevant molecules, it is possible to estimate which hydrogen bonds are most likely to take place between different molecules.   Different hydrogen bonds are assigned propensity scores which provides an avenue for predicting of co-crystals are likely to form between two different molecules and, if so, the type of intermolecular interactions that can be expected within the heteromeric co-crystal.  HBPC calculations were utilized to predict the likelihood of forming co-crystals between the anti-malarial drug pyrimethamine and carbamazepine, theophylline, aspirin, α-ketoglutaric acid, saccharin, coumaric acid, succinimide and L-isoleucine.  The HBPC agreed with the experimental observations indicating that this approach may offer effective and versatile tools for finding new solid forms of high-value chemicals such as pharmaceuticals and agrochemicals.   

H-bond prediction in pyrimethamine synthesis   

 

Complexities of mechanochemistry: elucidation of processes occurring in mechanical activators via implementation of a simple organic system
Adam A. L. Michalchuk, Ivan A. Tumanov and Elena V. Boldyreva 
CrystEngComm, 2013,15, 6403-6412   

Mechanochemistry is a current ‘hot topic’ which is of considerable interest to both covalent and supramolecular synthetic chemists.  A wide range of chemical transformations are now known to be possible using essentially ‘green’ reaction conditions.  Arguably, most papers that have presented in this field focus on proof-of-principle studies which demonstrate that “functional group ‘A’ can be converted to ‘B’ using the following reaction conditions”, but mechanistic or kinetic studies are still relatively uncommon.  In this paper, however,  Michalchuk et al, present a very detailed examination of the α-glycine : b-malonic acid system which include an analysis of how two key mechanical ‘forces’ – impact and shear – can influence reaction paths and product distribution.  This study clearly demonstrate that what actually happens in a ball mill or through a mortar-pestle treatment is likely to be far more complicated than what is assumed in most studies, notable the role played by the actual mechanoreactor itself.  The results are likely to be of critical importance to many mechanochemical reactions especially in the context of scale-up.   

Mechanochemistry    

 

Synthon identification in co-crystals and polymorphs with IR spectroscopy. Primary amides as a case study
Arijit Mukherjee, Srinu Tothadi, Shaunak Chakraborty, Somnath Ganguly and Gautam R. Desiraju 
CrystEngComm, 2013, 15, 4640-4654

It is probably fair to say that many crystal engineering efforts rely far too heavily on the use of single-crystal X-ray diffraction for product analysis and/or for interpreting the outcome of a particular crystallization or supramolecular synthesis.  However, in this paper, Desiraju and co-workers present a careful and informative study that correlates crystallography with vibrational spectroscopy.  In order to overcome the well-known challenges when using IR spectroscopy for analyzing polymorphs and co-crystals containing multiple synthons, the authors have employed a four-step approach that relies on the use of ‘spectral markers’ that can be directly associated with bonds in specific synthons.  The method is tested on an acid–phenol–pyridine co-crystal system and subsequently utilized for correctly identifying the different synthons in polymorphs of isonicotinamide.        

Synthons 

 

Halogen bond directionality translates tecton geometry into self-assembled architecture geometry
Marco Saccone, Gabriella Cavallo, Pierangelo Metrangolo, Andrea Pace, Ivana Pibiri, Tullio Pilati, Giuseppe Resnati and Giancarlo Terraneo 
CrystEngComm, 2013,15, 3102-3105 

This paper offers a particularly well-planned and carefully executed strategy for supramolecular synthesis.  One some level, this study may seem overly simplistic and the results may appear to be ‘obvious’ but this is, in my opinion, a testament to the progress that has been made in this field.  We sometimes forget that non-covalent synthesis has to rely on relatively weak and reversible interactions in an environment where solvent molecules are more than capable of disrupting solute-solute biding and, furthermore, that recrystallization is generally favored over heteromeric co-crystallizations.  The fact that we may think that the results presented herein are unsurprising simply means that we are making considerable progress towards finding and developing supramolecular reactions that display a robustness and reliability that we typically associate with named reactions in organic synthesis. 

Halogen bonds.   

 

 


ChristerAakeroy

Prof. Christer Aakeröy is a University Distinguished Professor at Kansas State University, Manhattan, KS, USA.  He is broadly interested in examining the way in which molecules recognize and bind to each other, and how they communicate and assemble into (occasionally) functional architectures.  He is currently the Chair of the Board of Governors for the Cambridge Crystallographic Data Centre and is an Associate Editor for CrystEngComm.

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CrystEngComm Editor’s choice

Control of the formation of rod-like ZnO mesocrystals and their photocatalytic properties
Yanqiang Yang, Yongqiang Yang, Haixia Wu and Shouwu Guo
CrystEngComm, 2013,15, 2608-2615 DOI: 10.1039/C2CE26429C

In this paper Y. Yang et al. demonstrate a simple synthesis approach towards ZnO mesocrystals. Rod-like ZnO mesocrystals consisting of ZnO nanoparticles have been prepared successfully through simply mixing the aqueous Zn(Ac)2 and NaOH in the presence of tartaric acid followed by high temperature annealing removing the organic linker. The reaction proceeded via a Zn(OH)2 precursor. It was demonstrated that several factors including the reaction temperature, the ratio of tartaric acid to Zn(Ac)2 in the reaction mixture and the annealing temperature could affect the morphology and structure of the mesocrystals. It was illustrated that the as-obtained ZnO mesocrystals have good stability and photocatalytic performance in photodegradation of methyl orange and photoreduction of Cr6+ in water. The best photocatalytic performance was reached for the mesocrystals annealed at 600 °C. This simple synthesis approach can be upscaled and might therefore become suitable for photocatalysis applications.

Control of the formation of rod-like ZnO mesocrystals and their photocatalytic properties

Oriented attachment growth of ultra-long Ag2Se crystalline nanowires via water evaporation-induced self-assembly
Chunyan Zeng, Weixin Zhang, Shaixia Ding, Zeheng Yang, Hui Zeng and Zhangcheng Li
CrystEngComm, 2013,15, 5127-5133 DOI: 10.1039/C3CE40232K

C. Zeng et al. demonstrated a synthesis method for ultra-long Ag2Se crystalline nanowires with lengths up to several hundred micrometers and diameters of 100–300 nm by a water evaporation-induced growth method at 120 °C for 6 h. The particle growth is mainly based on oriented attachment followed by subsequent nanoparticle fusion. The oriented attachment is based on secondary nucleation of small nanoclusters, which accumulate in the space between two nanoparticles as shown by HRTEM images. They are suggested to play an active role in the oriented attachment process. This study is an interesting extension of the oriented attachment concept of direct nanoparticle interaction and fusion since it involves a further step of secondary cluster nucleation, which then promote the oriented attachment process of the nanoparticles.

Oriented attachment growth of ultra-long Ag2Se crystalline nanowires via water evaporation-induced self-assembly

Surfactant-free CuO mesocrystals with controllable dimensions: green ordered-aggregation-driven synthesis, formation mechanism and their photochemical performances
Shaodong Sun, Xiaozhe Zhang, Jie Zhang, Liqun Wang, Xiaoping Song and Zhimao Yang
CrystEngComm, 2013,15, 867-877 DOI: 10.1039/C2CE26216A

Surfactant free approaches are of high interest in non-classical crystallisation to simplify the formation mechanisms. S.D. Sun et al. have demonstrated that the formation of CuO mesostructures is essentially determined by the characteristics of [Cu(OH)4]2− precursors. Oriented nanoparticle-aggregation with tailoring shapes in different dimensions can be achieved at moderate temperatures around 80 °C in water in different concentrations of reactants. The 3D “layer-by-layer” growth of mesocrystalline CuO spindles is successfully achieved at low concentrations of reagents, while the 2D “shoulder-by-shoulder” growth of mesostructural CuO plates is obtained at high reactant concentrations. This study is a nice example for bottom-up assembly of controllable ordered mesocrystalline architectures without any organic additive based on TEM / HRTEM investigations. It offers a good opportunity to understand the formation mechanism and growth process of surfactant-free CuO mesostructures with controllable aggregation-based behaviour. In addition, photocatalytic properties of the obtained CuO mesocrystals are reported.

Surfactant-free CuO mesocrystals with controllable dimensions: green ordered-aggregation-driven synthesis, formation mechanism and their photochemical performances

Template-free facile solution synthesis and optical properties of ZnO mesocrystals
Sha-Sha Wang and An-Wu Xu
CrystEngComm, 2013,15, 376-381 DOI: 10.1039/C2CE26638E

This study is another interesting example of mesocrystal synthesis without added organic molecules, which are usually the basis for mesocrystal formation. However, since the reaction was performed in butanol in an autoclave, the butanol can serve as additive itself. The ZnO mesocrystal microspheres as well as stacks of hexagonal platelets were assembled with primary hexagonal nanoplatelets. Intrinsic dipole–dipole interactions between the specific (001) countercharged faces of the ZnO nanocrystals play an important role in this mesoscale transformation. These mesocrystals are a typical example for a dipole driven mechanism resulting in a mesocrystalline structure determined by the dipole field lines of a primary dipole, rather than a perfect 3D aligned nanoparticle structure.

 Template-free facile solution synthesis and optical properties of ZnO mesocrystals

Top-down fabrication of hematite mesocrystals with tunable morphologies
Jinguang Cai, Suyue Chen, Jun Hu, Zhi Wang, Yurong Ma and Limin Qi
CrystEngComm, 2013,15, 6284-6288 DOI: 10.1039/C3CE40414E

This paper is a fascinating demonstration that mesocrystals can also be fabricated by top down approaches rather than by the bottom up self assembly approaches which everyone associates with mesocrystals.

Hematite mesocrystals with tunable morphologies by selective HCl etching of hematite pseudocubes are reported, which is the first shape-controlled fabrication of mesocrystals via chemical etching. Particularly, porous hematite mesocrystals with unique cone-like and sandglass-like morphologies were produced from micron-sized pseudocubes (or microcubes) while disc-like hematite mesocrystals were obtained from submicron-sized pseudocubes (or submicrocubes). This study therefore opens an entirely new and simple pathway towards mesocrystalline structures. In addition, the obtained hematite mesocrystals exhibited enhanced visible-light photocatalytic activity and high Cr(VI) removal capacity.

Top-down fabrication of hematite mesocrystals with tunable morphologies

Self-assembly of magnetite mesocrystal microdisks with hierarchical architectures
Ruimin Yao, Chuanbao Cao and Ju Bai
CrystEngComm, 2013,15, 3279-3283 DOI: 10.1039/C3CE26949C

A related etching based method towards mesocrystals is reported by R.M. Rao et al. The authors start from an iron foil which is transformed into mesocrystals of magnetite microdisks under hot and concentrated alkaline conditions by employing oxygen adsorption corrosion. The self-assembled magnetite mesocrystal microdisks have displayed crystalline three-dimensional superstructures. The large size of one formed microdisk is about 30 μm, composed of many 20 nm small nanoparticles. These nanoparticles first self-assembled as thin layers, then the thin layers further self-assembled to a microdisk. All these structures show a new approach towards mesocrystals synthesis.

 Self-assembly of magnetite mesocrystal microdisks with hierarchical architectures

A facile solid phase reaction to prepare TiO2 mesocrystals with exposed {001} facets and high photocatalytic activity
Li Zhou, Jin Chen, Chuan Ji, Lei Zhou and Paul O’Brien
CrystEngComm, 2013,15, 5012-5015 DOI: 10.1039/C3CE27095E

In this paper Zhou et al. utilise the solid–solid topotactic transformation of NH4TiOF3 to anatase TiO2 by a simple sintering process. In order to obtain the exposed {001} facets on the surfaces of final products, the sintering temperature must be between 700 °C and 900 °C. The approach is flexible, controllable, greener and easier in comparison with widely-used hydrothermal methods. The photocatalytic activity of the obtained TiO2 mesocrystals is much higher than that of the corresponding TiO2 polycrystalline materials. The exposed {001} facets are believed to play a very important role in the photocatalysis process.

 A facile solid phase reaction to prepare TiO2 mesocrystals with exposed {001} facets and high photocatalytic activity

Effect of bulk pH and supersaturation on the growth behavior of silica biomorphs in alkaline solutions
Josef Eiblmeier, Matthias Kellermeier, Doris Rengstl, Juan Manuel García-Ruiz and Werner Kunz
CrystEngComm, 2013,15, 43-53 DOI: 10.1039/C2CE26132D

The last highlighted study concerns the fascinating nanoparticle hybrid superstructures found as the so-called “Biomorphs”. This study shows that co-precipitation of witherite and silica affords crystal aggregates with complex curved morphologies only if the starting pH of the mother solution is adjusted to values within a certain window, which was found to range from pH 10.2 – 11.1. At both lower and higher initial pH, only fractal architectures, resulting from self-similar branching of the carbonate crystal core, were obtained. In situ time dependent measurements of the bulk pH and Ba2+ concentration, enabled the absolute values for the actual supersaturation of the system at distinct growth stages to be calculated. This allows for a deeper understanding of the growth mechanism of these complex materials.

 Effect of bulk pH and supersaturation on the growth behavior of silica biomorphs in alkaline solutions


Helmut CoelfenProf. Dr. Helmut Cölfen is currently the Professor of Physical Chemistry at the University of Konstanz, Germany. His research interests include non-classical crystallisation, synthesis of organic-inorganic hybrid colloids with complex forms, synthesis of amphiphilic functional block copolymers, and fractionating methods for colloid and polymer analysis.

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