Archive for the ‘Hot Article’ Category

Hot Highlight: Porous organic molecular materials

Metal–organic frameworks are materials containing coordination bonds between organic linkers and metal ions or clusters, exclusion of guest molecules in the structure can create a highly porous material with potential for gas storage, gas separation or catalysis. Other well studied nanoporous materials include zeolites, metal oxide molecular sieves, silica gels, activated carbons, covalent organic frameworks and organic network polymers.

This highlight from Jian Tian, Praveen K. Thallapally and B Peter McGrail from Pacific Northwest National Laboratory reviews a very different class of nanoporous material, those comprised entirely of discrete organic molecules containing only weak non-covalent interactions. Often there is very close packing in the crystals (with voids or channels rarely exceeding 25 Angstroms) but under the right conditions solvents can be included within the structure in zero, one, two or three dimensional solvent accessible voids.

If the solvent can be easily removed from the structure highly porous crystalline materials can be made  from organic compounds, the difficulty however is that upon desolvation the crystals often collapse into closely packed structures. This review discusses a wide range of structures which have been found to be stable as porous organic molecular materials, including crystalline structures with voids and amorphous solids with interconnected disordered pores. Read the CrystEngComm Hot Article (which is free to access for 4 weeks) for more details.

Porous organic molecular materials
Jian Tian, Praveen K. Thallapally and B Peter McGrail
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE06457J, Highlight

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Hot Article: Polar Crystals

‘To get a polar crystal is still a challenging task,’ say Roberto Centore and colleagues. However in their CrystEngComm Hot article they in fact tell us about the discovery of a new class of non-chiral compounds forming polar crystal structures.

Their compounds are made by condensation of 4-hydroxybenzohydrazide with a variety of non-chiral aliphatic ketones, both cyclic and acyclic, such as methyl-ethylketone, acetone, cyclohexanone and cyclobutanone and all of them exhibit second harmonic generation (SHG) activity. In one case, they found that solid state polymorphism characterized by single-crystal-to-single-crystal transitions between polar phases was taking place.

Read their paper now – free to access until the 4th February:

A series of compounds forming polar crystals and showing single-crystal-to-single-crystal transitions between polar phases
Roberto Centore, Mojca Jazbinsek, Angela Tuzi, Antonio Roviello, Amedeo Capobianco and Andrea Peluso
CrystEngComm, 2012, DOI: 10.1039/C2CE06352B

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HOT Communication: Enhancing the clinical performance of tadalafil through crystal engineering

Pharmaceutical cocrystals of tadalafil with methylparaben, propylparaben and hydrocinnamic acid were investigated.

Pharmaceutical cocrystals of tadalafil with methylparaben, propylparaben and hydrocinnamic acid were investigated.

A team from the United States report their study on the hydrogen bonding motifs in tadalafil cocrystals with the aim to produce a drug with enhanced solubility for better oral drug absorption.  Tadalafil, currently used for the treatment of erectile dysfunction, is being explored as a treatment for pulmonary arterial hypertension so would be more useful for this application if the time taken to reach its peak plasma concentration was shorter.

To find out more, download this CrystEngComm communication today…

Crystal engineering of multiple-component organic solids: Pharmaceutical cocrystals of tadalafil with persistent hydrogen bonding motifs
David R. Weyna, Miranda L. Cheney, Ning Shan, Mazen Hanna, Lukasz Wojtas and Michael J. Zaworotko
CrystEngComm, 2012
DOI: 10.1039/C2CE06574F

The communication by Zaworotko et al. will be published later in the year as part of a themed issue on crystal engineering in the pharmaceutical industry.  Below is a selection of papers also due to be included in this themed issue:

Covalent assistance to supramolecular synthesis: modifying the drug functionality of the antituberculosis API isoniazid in situ during co-crystallization with GRAS and API compounds
Andreas Lemmerer
CrystEngComm, 2012
DOI: 10.1039/C1CE06310C

Effect of dehydration on the mechanical properties of sodium saccharin dihydrate probed with nanoindentation
M. S. R. N. Kiran, Sunil Varughese, U. Ramamurty and Gautam R. Desiraju
CrystEngComm, 2012
DOI: 10.1039/C1CE05656E

Solid state chemistry of the antibiotic doxycycline: structure of the neutral monohydrate and insights into its poor water solubility
Alexandre O. Legendre, Laila R. R. Silva, Douglas M. Silva, Iara M. L. Rosa, Lilian C. Azarias, Polyana J. de Abreu, Magali B. de Araújo, Person P. Neves, Claudia Torres, Felipe T. Martins and Antonio C. Doriguetto
CrystEngComm, 2012
DOI: 10.1039/C1CE06181J

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Polymorphs and proline: implications for polymorphic screening in Pharma

The particular form a crystalline drug takes is highly relevant in the pharma industry as different crystal forms often have different properties such as dissolution rates or stabilities. Though crystallisation processes are commonplace in the production of enantiopure drugs, the way in which one enantiomer can affect the crystallisation of another has not be thoroughly studied.

In their recent CrystEngComm Hot Article, Munson and Berendt carry out such a study investigating proline enantiomers in a range of enantiomeric ratios. They determine that both the enantiomeric ratio and crystallization method influenced the polymorphism of the racemic cocrystal. Read how their work will have implications for current polymorphic screening methods used in the pharma industry in their article:

Effect of enantiomeric ratio and preparation method on proline crystal form
Robert T. Berendt and Eric J. Munson
CrystEngComm, 2012, DOI: 10.1039/C2CE06445F

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HOT Highlight: Zr(IV)-based metal–organic frameworks

This comprehensive Highlight by Min Kim and Seth Cohen outlines the discovery, development and functionalization of Zr(IV)-based metal–organic frameworks. MOFs in general have been widely studied and the potential in biotechnological applications, catalysis, chemical sensing, gas separation and gas storage is of great interest.

Zr(IV)-based MOFs were discovered in 2008 and in that short period substantial research has been undertaken with more than forty functionalised Zr(IV)-based MOFs discovered. This review looks in detail at the synthesis, functionalization and application of this relatively new addition to the MOF family. The authors note the great potential for Zr(IV)-based MOFs, including applications in catalysis, photo-chemical reactions and molecular separations.

To find out more access this article free for the next 4 weeks

This article will be published later in the year in a CrystEngComm themed issue focussing on post-synthetic modification of coordination networks.

Discovery, development, and functionalization of Zr(IV)-based metal–organic frameworks
Min Kim and Seth M. Cohen
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE06491J, Highlight

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Herding? You’ll need either a dog, a pig, or HFB

 

Magnetism in organic crystal structures can be quite a complex property and understanding it’s subtleties is an intense field of study. This HOT Highlight in CrystEngComm details the magnetic properties and crystal structures of functionalized pyrene radicals, Paul M. Lahti et al. found that different polymorphs led to different magnetic properties and that intermolecular distances of NO—ON contacts played a key role in the resultant magnetism. The authors also discovered they could ‘shepherd’ molecules by adding hexafluorobenzene (HFB), altering the stacking and intermolecular contacts resulted in different exchange interactions between the radical molecules. In the co-crystal they observed a weaker but further extending magnetic behaviour, showing how rational manipulation of crystallisation conditions can lead to controlled magnetic properties.

Read the full Highlight which is free to access for 4 weeks in CrystEngComm

Radicals organized by disk shaped aromatics – polymorphism and co-crystals that tune inter-electron exchange
Handan Akpinar, Joel T. Mague, Miguel A. Novak, Jonathan R. Friedman and Paul M. Lahti
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C1CE06096A

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Hot Article: High quality, without phase separation – progress in a-plane MgZnO epilayer growth

Resonant Rutherford backscattering spectrometry along with with ion channeling revealed a uniform growth in both composition and atomic order.

Andrés Redondo-Cubero and colleagues detail the growth of high-quality thick a-plane MgZnO epilayers that can be grown without phase-separation but that contain greater than 50% Mg. The team also constructed Au-MgZnO photodiodes to test if the layers could be used in optoelectronic devices, giving positive results.

To find out more, download this CrystEngComm paper today…

Single phase a-plane MgZnO epilayers for UV optoelectronics: substitutional behaviour of Mg at large contents
A. Redondo-Cubero, A. Hierro, J.-M. Chauveau, K. Lorenz, G. Tabares, N. Franco, E. Alves and E. Muñoz
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE06315H

You might also find this paper interesting:

Density and aspect ratio controlled MgZnO nanowire arrays by spontaneous phase separation effect
Dong Chan Kim, Ju Ho Lee, Sanjay Kumar Mohanta, Hyung Koun Cho, Hyoungsub Kim and Jeong Yong Lee
CrystEngComm, 2011, 13, 813-818
DOI: 10.1039/C0CE00114G

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HOT Article: Superior tableting from ionised amide groups

This HOT article reports the first salt form of acetaminophen, which is shown to have superior tableting properties relative to the stable polymorph of the unionised drug.  Amide groups are generally considered non-ionisable for the purposes of drug development and there are only a handful of  crystal structures with ionised amide groups known.  This success of forming an amide–hydrochloride salt using a simple experimental protocol may well encourage other research groups, both industrial and academic, to attempt salt formation with amides.

Read more about this important contribution to solid-state chemistry for FREE until 10th January 2012 at:
Ionized form of acetaminophen with improved compaction properties
Sathyanarayana Reddy Perumalla, Limin Shi and Changquan Calvin Sun
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C1CE06278F

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We can’t predict snow but can we predict melting points?

Computational inorganic chemistry has been providing significant insight into understanding chemical interactions and properties for some time now and the fruits of this labour are likely to become more in-depth and frequent as technologies advance. Simon Grabowsky et al. have been investigating the crystal packing in a series of naphthodioxanes which they systematically modified to possess larger R-groups and characterised the crystal structures of the materials at 100K.

The team also performed Hirshfeld surface analysis (a definition of molecular boundaries and intermolecular interactions) on their series of compounds and were able to correlate the surface analysis information with the crystal melting points. The team used molecules that don’t contain the traditional H-bond donor functional groups such as N-H and O-H so they were able to distinguish between the effects of different types of weaker interactions.

You can read the full details of this insightful investigation by accessing the full paper which is free for 4 weeks.

The Dalton Transactions themed issue ‘Computational chemistry of inorganic systems’ might also be of interest!

Crystal packing in the 2-R,4-oxo-[1,3-a/b]-naphthodioxanes – Hirshfeld surface analysis and melting point correlation
Simon Grabowsky, Pamela M. Dean, Brian W. Skelton, Alexandre N. Sobolev, Mark A. Spackman and Allan H. White
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE06393J

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Electrostatic potential in drug design

With bacterial resistance to established broad-spectrum antibiotics on the increase, detailed understanding of antibacterial action and drug resistance mechanisms are urgently needed. This understanding enables success in structure based drug design of novel bacterial topoisomerase inhibitors. In their CrystEngComm paper Birger Dittrich and co-workers discuss why molecular electrostatic potentials are key for rational drug design. They look at the optimization of structures on the basis of a comparison of nine fluoroquinolone antibiotics.

Electrostatic properties of nine fluoroquinolone antibiotics derived directly from their crystal structure refinements
Julian Jacob Holstein, Christian Bertram Hübschle and Birger Dittrich
CrystEngComm, 2012, DOI: 10.1039/C1CE05966A

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