Predicting properties of ionic liquids

It is now possible to accurately predict the density, refractive index and molar polarisability of any imidazolium-based ionic liquid thanks to the recent work of Schröder et al.

Given the availability of at least one million simple ionic liquids, predicting which ionic liquid is best suited to a given application is a significant task. Molar polarisability is a key factor in describing solvation effects and, in principle, can be determined by various quantum-mechanical methods. However, these methods are Polarisabilities of ionic liquidstime-consuming and can only be applied to a small subset of ionic liquids.

Schroder et al. used a Designed Regression Analysis to deconstruct the molar polarisability and molar volume into atomic contributions in this recent PCCP article. They used their approach to explore how the refractive indices of various imidazolium-based ionic liquids were influenced by the length of the alkyl chains.

Read the full PCCP article today:

Polarisabilities of alkylimidazolium ionic liquids
Christian Schröder, Katharina Bica, Maggel Deetlefs and Kenneth R. Seddon
DOI: 10.1039/C3CP43867H

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Micro-structure of solvents

Thomas Just Sørensen is a guest web-writer for PCCP. He is currently a post-doctoral researcher at the University of Copenhagen, Denmark.

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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New PCCP Associate Editor: Dr Ajayaghosh

New PCCP Associate Editor Dr Ayyappanpillai AjayaghoshWe are extremely pleased to annouce that Dr Ayyappanpillai Ajayaghosh is a new Associate Editor for Physical Chemistry Chemical Physics (PCCP). His research interests include supramolecular chemistry, chemosensors, low band-gap polymers, fluorescent gels, organic nanostructures and photoresponsive systems.

Dr Ajayaghosh is a CSIR Outstanding Scientist at the National Institute for Interdisciplinary Science and Technology (NIIST), India. He completed his PhD at the University of Calicut after graduating from Kerala University with a BSc. He has received numerous awards including  the Infosys Prize (2012) for his outstanding contribution in the field of physical sciences, and in particular for his work that has advanced supramolecular chemistry.

Dr Ajayagosh will begin handling papers soon and so we encourage you to submit to his editorial office.

Read Dr Ajayaghosh’s paper in the PCCP themed issue on materials innovation through interfacial physics and chemistry:

Excitation energy migration in oligo(p-phenylenevinylene) based organogels: structure-property relationship and FRET efficiency
Chakkooth Vijayakumar, Vakayil K. Praveen, Kalathil K. Kartha and Ayyappanpillai Ajayaghosh
DOI: 10.1039/C0CP02110E

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Not-so innocent interactions of oxide-surfaces

In this insightful and well-rounded review, Gianfranco Pacchioni summarises the latest knowledge regarding the metal/oxide interface. Such knowledge has become crucial in the elucidation of reaction mechanisms and catalytic properties of metal-oxide catalysts.

Thanks to increasingly sophisticated techniques, it has become known that the original chemical and structural properties of a metal nanoparticle deposit can be significantly altered upon interaction with an oxide support. Particularly for catalysts containing metal nanoparticles smaller then about 1 nm, the phenomenon is particularly significant and somewhat complex.Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces

For a long time, it was assumed that the oxide component of heterogeneous catalysts provided an “inert” support. Pacchioni takes us through the experimental and theoretical evidence that has shown that the support is in fact not as “innocent” as first thought, and focuses on the nature of the chemical bonds formed between metal atoms and clusters and oxide surfaces.

Read this PCCP Perspective in full today:

Electronic interactions and charge transfers of metal atoms and clusters on oxide surfaces
Gianfranco Pacchioni
DOI: 10.1039/C2CP43731G

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Understanding nanoparticle surface electromagnetic fields

US Scientists have successfully used second harmonic generation (SHG) measurements to probe the complicated plasmon resonances arising from inter-particle interactions within nanoparticle networks.

Kenneth Knappenberger Jr. and Manabendra Chandra from Florida State University performed systematic polarization-resolved single-particle SHG measurements on solid gold nanosphere dimers.  In addition, continuous polarization variation (CPV) experiments were used to obtain single particle non-linear optical data. They were able to demonstrate the superiority of their technique over measurements that rely exclusively on linearly polarized light to study structure-specific plasmonics.single particle non-linear optical spectroscopy to study nanoparticle surface electromagnetic fields

A large SHG depolarization ratio was measured when the two nanoparticles forming a dimer were in close vicinity of each other. CPV spectra of single dimers revealed large inter-dimer variations, which can only be described by including magnetic-dipolar interactions.

Their work represents an important step towards a predictive understanding of the optical properties of nanostructured materials.

Read this HOT PCCP article today:

Nanoparticle surface electromagnetic fields studied by single-particle nonlinear optical spectroscopy
Manabendra Chandra and Kenneth L. Knappenberger
DOI: 10.1039/C2CP43271D, Paper

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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

Victoria Wilton is a guest web-writer for PCCP. She is currently studying for a PhD at the University of Nottingham, UK.

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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New PCCP Associate Editor Prof. Gaoquan Shi

Photograph of Gaoquan ShiWe are delighted to welcome Professor Gaoquan Shi as a new Associate Editor for Physical Chemistry Chemical Physics (PCCP). His research interests are focused on functional polymers, especially the syntheses and applications of conducting polymers and carbon nanomaterials.

Professor Shi has been a professor of Chemistry at Tsinghua University since 2000. In 2004,  he received the 2nd grade award of Natural Science of China and the youth knowledge innovation prize of Chinese Chemical Society and BASF Company.

Professor Shi will start handling papers soon and so we encourage you to submit to his editorial office.

Read some of Professor Shi’s recent articles in PCCP:

Synthesis of gold@carbon dots composite nanoparticles for surface enhanced Raman scattering
Peihui Luo, Chun Li and Gaoquan Shi
DOI: 10.1039/C2CP40767A

Supercapacitors based on self-assembled graphene organogel
Yiqing Sun, Qiong Wu and Gaoquan Shi
DOI: 10.1039/C1CP22409C

High-performance supercapacitor electrodes based on graphene hydrogels modified with 2-aminoanthraquinone moieties
Qiong Wu, Yiqing Sun, Hua Bai and Gaoquan Shi
DOI: 10.1039/C1CP20980A

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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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