Author Archive

Micro-structure of solvents

We know much about the energetics in solutions and of species in solution. We can directly measure most parameters, when we measure energy. When it comes to the structure of solution or in solutions, we know next to nothing. Indirect measurements are our main source of information, as we cannot see the fluctuating solution structures. Miyuki Tanaka and co-workers have performed one of the most informative studies using indirect methods to probe solvent structures that I have come across.

In a recent paper in PCCP by Miyuki Tanaka, Tomoaki Yago and Masanobu Wakasa the microscopic structure of ionic liquid solvents is investigated. The diffusion of single particles is compared to the macroscopic measure of viscosity. They find that the ionic liquids are ‘more sticky’, when looking at the diffusion of single molecules, than more commonly used solvents; although the viscosities of the two solvents are identical.

In “Local structure of ionic liquids probed by self-quenching of thiobenzophenone” the movement of single microscopic particles in solution (molecular diffusion), are compared to measurement determining how difficult a macroscopic object moves in the same solution (the viscosity). A single particle is excited using light and gains energy. The energy can be released the by collision with another particle in the solution.  By following the evolution of the population of excited particles the molecular movements can be followed.

The result presented in this paper is another piece of the puzzle we have to assemble in order to understand the microstructure of solvents, and the conundrum of solvation. Solvents are everywhere, most ubiquitous is water. We have a limited understanding of the structure of pure solvents, and know even less about the structure of complex solutions. The collection of small molecules that constitute most liquids can have an astoundingly complex structure. A structure that we have to know and understand, if we are to comprehend the complex condensed phases such as the cells that make up most living things.

At the most advanced facility for structural investigation of matter, the SLAC national accelerator laboratory, an entire team of elite scientists has been assembled ‘just’ to elucidate the structure of water. The method applied by Tanaka and co-workers is a much simpler route to understanding molecular movements in solution. When a large library of different solvents has been investigated, we will be able to deduce effects of specific solvation. Following this, we may be able to explain exactly why the ionic liquids are ‘more sticky’ than traditional solvents.

Local structure of ionic liquids probed by self-quenching of thiobenzophenone” by Miyuki Tanaka, Tomoaki Yago and Masanobu Wakasa was published in Physical Chemistry Chemical Physics (PCCP) at the beginning of 2013: M. Tanaka, T. Yago, M. Wasaka Phys. Chem. Chem. Phys.2013, 15, 787-794

By Dr Thomas Just Sørensen

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PCCP Board member reflects on the future of chemistry research in India

PCCP Advisory Board member Professor Elangannan Arunan has co-authored a report in Angewandte Chemie on the excellent potential of Indian chemistry and how it can be best realised.

The authors ideas include improving access to start-up grants for new faculty members and encouraging the funding of new, untested ideas.

Check out these excellent PCCP Perspectives (co-)authored by researchers working in India:

Design and development of quantum dots and other nanoparticles based cellular imaging probe

Nikhil R. Jana
DOI: 10.1039/C0CP00726A

Do N-heterocyclic aromatic rings prefer π-stacking?
Mridula Guin , G. Naresh Patwari , S. Karthikeyan and Kwang S. Kim
DOI: 10.1039/C0CP02015J

The hydrogen bond: a molecular beam microwave spectroscopist’s view with a universal appeal
Mausumi Goswami and E. Arunan
DOI: 10.1039/B907708A

You may also be interested to read Prof. Arunan’s “Editor’s Choice” selection of articles in PCCP on a theme of bonding, reaction kinetics and dynamics.

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The surprising chemistry of the noble gases

The inherent lack of reactivity of the noble gases is so entrenched in the collective mind of the population, that even though noble gas containing compounds have been known for decades, the identification of new ones is still extremely exciting. I was therefore delighted to come across this particular article in PCCP.

Fernández and Frenking conducted a theoretical investigation into the stability and nature of the bonding involved in two classes of compounds containing a Xe-Xe bond. No species from either of the two groups, HXeXeX (where X=halogen) and RXeXeR’ (where R and R’ are both halogens), have ever been observed experimentally, and based on their results, several compounds for which this might be possible were identified.

The strong correlation observed between Xe-Xe bond length and the energy barrier to decomposition suggests that the strength of this bond plays a vital role in the stability of the molecule. Both of these characteristics were shown to decrease with increasing halogen mass, and generally indicated stronger bonding and greater stability in the RXeXeR’ molecules compared with HXeXeX. On this basis, HXeXeF and FXeXeF were proposed as the most viable compounds for experimental isolation.

The former was shown to be the result of two electrostatically bonded fragments, HXeXe+ F, with a strong covalent H-Xe bond. The positive charge is shared over the two Xe atoms, with the smaller proportion on the Xe next to the F atom. The Xe-Xe bond in this case is thought to be primarily electrostatic, and involve only the px orbital. By analogy, FXeXeF could either be formed of similar electrostatically bonded fragments, or through the interaction of two FXe· radicals. The calculations pointed to contributions from both mechanisms, with a small but significant bias toward radical interaction.

This research represents another step in unravelling and understanding the complicated and often surprising chemistry of the noble gases. It would therefore be marvellous to see experimental confirmation of their findings in the future.

By Victoria Wilton

Read the full details of this fascinating article which was published as part of the PCCP themed issue on Predicting new molecules by quantum chemical methods:

Neutral noble gas compounds exhibiting a Xe–Xe bond: structure, stability and bonding situation
Israel Fernández and Gernot Frenking
DOI: 10.1039/C2CP41244F

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Understanding the interaction of C60 with red blood cells to guide therapeutic use of nanomaterials

Carbon nanomaterials have been hailed as potential drug carriers and biosensors, so it is important to understand how they interact with human cells. Scientists in China have studied the interaction of C60 nanoparticles (NPs) with human red blood cells and found that they made the cell membrane become “softer and easier to break”. They were able to successful model this, and predict the effect of a given amount of NPs. The finding could be used to determine appropriate dosage levels of C60 NPs in medical applications for maximum therapeutic effect with the minimum toxicity.

Read more about this fascinating work in this HOT PCCP article:

Mechanical characteristics of human red blood cell membrane changing due to C60 nanoparticles infiltration
Yue Zheng
DOI: 10.1039/C2CP42850D

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PCCP themed issue: Superresolution imaging and fabrication with light

Superresolution imaging and fabrication with light
Guest Editors: Françisco M. Raymo (University of Miami, USA)

PCCP is delighted to announce the high-profile themed issue ‘Superresolution imaging and fabrication with light’. It is our pleasure to invite you to submit to this themed issue.

The themed issue will be published in PCCP in  2013 and will be promoted to the community throughout the year to maximise the visibility of the work published.

Deadline for Submissions: 8 April 2013

Diffraction prevents the focusing of light within volumes of subwavelength dimensions. As a result, this unavoidable physical phenomenon limits the resolution of imaging and lithographic techniques based on far-field optics. In order to overcome these stringent limitations, significant research efforts have been directed, over the past decade, to the identification of protocols to overcome diffraction.

Some of these methods rely on the photochemical and photophysical properties of engineered chromophores to circumvent diffraction. These clever operating principles have already succeeded in bringing the resolution of fluorescence imaging and photolithography down to the nanoscale. Indeed, they are starting to impact biomedical research and, presumably, will soon have similar implications in information technology.

Thus it is timely to publish a themed collection in PCCP on this emerging and extremely promising area of research. The themed collection will provide a general overview of the fundamental principles of these strategies as well as covering optical imaging and fabrication at the nanoscale.

It is essential that all submissions to PCCP should contain new physical insight and contributions to this themed collection will be assessed on this basis.

  • Manuscripts can be submitted in any reasonable format using our online submissions service
  • Submissions should be high quality manuscripts of original, unpublished research
  • Communications and full papers can be submitted for consideration, which will be subject to rigorous peer review
  • Please indicate upon submission that your manuscript is intended for this themed is intended for the themed issue

Please contact the PCCP Editorial Office to let us know you plan to contribute an article.

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Physical-chemistry at the cross-road of advanced oxide materials

PCCP themed issue: call for papers

Physical-chemistry at the cross-road of advanced oxide materials
Guest Editors: Flora Boccuzzi (University of Torino), Leonardo Marchese (University of Piemonte Orientale “A. Avogadro”) and Gianmario Martra (University of Torino)

PCCP is delighted to announce the high-profile themed issue on advanced oxide materials. It is our pleasure to invite you to submit to this themed issue.

The themed issue will be published in PCCP in  2013 and will be promoted to the community throughout the year to maximise the visibility of the work published.

Deadline for Submissions: 18 March 2013

Oxide-based materials have been largely studied for their catalytic, electronic or adsorbent properties. Since the early 1960’s, when studies of high surface area oxides and metal dispersed on oxides of interest for catalysis and sensing were mostly developed, their interest has been extended along the years to other technological applications such as energy production, biotechnology and nanomedicine. In general, the broad range of emerging applications has pushed the preparation of new functional oxide-based materials, with expected tailored smart properties.

This themed issue is intended to highlight the central role of experimental and theoretical physical-chemical investigations of bulk and surface structural and functional properties of these materials to target actual, knowledge-based breakthroughs.

Topics covered by this themed issue include experimental and/or theoretical studies of:

  • structure of surface sites of heterogeneous catalysts by in-situ/in-operando methods;
  • mechanisms of reactions of interest for sustainable chemical processes and catalyzed by oxide-based materials;
  • molecular or photophysical events occurring at the surface/interface of nanomaterials for energy production;
  • understanding physico-chemical phenomena of oxide-based materials for energy production, storage and emission;
  • physico-chemical characterization of functional-oriented materials for sensing;
  • physico-chemical studies of the interaction of oxide-based materials with biomolecules;
  • unconventional spectroscopic studies.

Contributions on oxide-based materials outside the above list of topics will be also accepted provided that they are within the scope of PCCP and contain sufficient new physical insight.

  • Manuscripts can be submitted in any reasonable format using our online submissions service
  • Submissions should be high quality manuscripts of original, unpublished research
  • Communications and full papers can be submitted for consideration, which will be subject to rigorous peer review
  • Please indicate upon submission that your manuscript is intended for this themed is intended for the themed issue

Please contact the PCCP Editorial Office to let us know you plan to contribute an article.

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Understanding bonding in new inorganic clusters

Ajournal cover image paper from the recent PCCP themed issue on Predicting new molecules by quantum chemical methods has been highlighted in UCLA today. The article by Anastassia Alexandrova and her coworkers was featured on the back cover of the issue and describes the authors work on using computational methods to discover new inorganic clusters and understand their bonding.

Read this interesting PCCP paper today:

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−

Anastassia N. Alexandrova Michael J. Nayhouse Mioy T. Huynh Jonathan L. Kuo Arek V. Melkonian Gerardo Chavez Nina M. Hernando Matthew D. Kowal and Chi-Ping Liu
Phys. Chem. Chem. Phys., 2012, 14, 14815-14821

DOI: 10.1039/C2CP41821E

Selected AB42−/− (A = C, Si, Ge; B = Al, Ga, In) ions: a battle between covalency and aromaticity, and prediction of square planar Si in SiIn42−/−
Anastassia N. Alexandrova, Michael J. Nayhouse, Mioy T. Huynh, Jonathan L. Kuo, Arek V. Melkonian, Gerardo Chavez, Nina M. Hernando, Matthew D. Kowal and Chi-Ping Liu
DOI: 10.1039/C2CP41821E

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Combined theoretical and experimental approach identifies ideal nerve gas capture agent

Scientists working in Australia, Poland and the USA have come up with a combined theoretical and experimental approach for screening candidate materials that could be used to capture nerve gas agents. They conclude that the ideal material contains slit-shaped pores of around 0.5 nm width.

Their PCCP paper was highlighted on the nanowerk website. Read the article today:

Screening of Carbonaceous Nanoporous Materials for Capture of Nerve Agents
Piotr Kowalczyk, Artur Piotr Terzyk, Piotr A. Gauden and Alexander V Neimark
DOI: 10.1039/C2CP43366D

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Dreaming of new and unusual molecules

Table of contents imageIn this fascinating PCCP Perspective Alexander Ivanov and Alexander Boldyrev describe progress in using theoretical methods to predict unusual new molecules that can potentially be made for real in the experimental lab.

They suggest that emerging methods for predicting exciting materials and clusters will allow the field to develop in new directions in the coming years.

Read this PCCP Perspective article in full today:

Reliable predictions of unusual molecules
Alexander S. Ivanov and Alexander I. Boldyrev
DOI: 10.1039/C2CP42877F

If you enjoyed this article you may also be interested in our recent themed issue on Predicting new molecules by quantum chemical methods, Guest Edited by Gabriel Merino and Thomas Heine.

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New finding throws doubt on interpretation of single molecule fluorescence imaging data

Single molecule fluorescence measurements hold great promise for studying biological processes on a very small scale. These experiments are typically conducted using a scanning confocal fluorescence microscope.

The data rely on the focusing of excitation light to a specific point on a molecule, with the fluorescence output being collected using the same objective lens. The fluorescence output can be varied by changing the external electric field. But an out-of-focus excitation light, say scientists in Singapore, due to the not uncommon occurrence of damage to the type of thin film devices used in such experiments, can result in a decrease in the output fluorescence – which could potentially be misinterpreted as a significant effect.

The results indicate that researchers measuring fluorescence modulation using this electric field method should be aware that this type of artefact could interfere with their results.

Read more details about these interesting findings:

Other origins for the fluorescence modulation of single dye molecules in open-circuit and short-circuit devices
Edwin Yeow, Jefri Sanusi Teguh, Michael Kurniawan, Xiangyang Wu and Tze Chien Sum
DOI: 10.1039/C2CP43284F

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