Chemical Science Blog

Take a look at this selection of recently published referee-recommended articles – all are open access and free to read:

Latent harmony in dicarbon between VB and MO theories through orthogonal hybridization of 3σ_g and 2σ_u
Ronglin Zhong, Min Zhang, Hongliang Xu and Zhongmin Su
DOI: 10.1039/C5SC03437J, Edge Article

Rational design of a water-soluble, lipid-compatible fluorescent probe for Cu(I) with sub-part-per-trillion sensitivity
M. T. Morgan, A. M. McCallum and C. J. Fahrni
DOI: 10.1039/C5SC03643G, Edge Article

Targeting antioxidant pathways with ferrocenylated N-heterocyclic carbene supported gold(I) complexes in A549 lung cancer cells
J. F. Arambula, R. McCall, K. J. Sidoran, D. Magda, N. A. Mitchell, C. W. Bielawski, V. M. Lynch, J. L. Sessler and K. Arumugam
DOI: 10.1039/C5SC03519H, Edge Article

Mesoporous Pt nanospheres with designed pore surface as highly active electrocatalyst
Bo Jiang, Cuiling Li, Victor Malgras, Masataka Imura, Satoshi Tominaka and Yusuke Yamauchi
DOI: 10.1039/C5SC03779D, Edge Article

Many Mg–Mg bonds form the core of the Mg₁₆Cp^*₈Br₄K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
T. Kruczyński, F. Henke, M. Neumaier, K. H. Bowen and H. Schnöckel
DOI: 10.1039/C5SC03914B, Edge Article

Thermodynamic synthesis of solution processable ladder polymers
Jongbok Lee, Bharath Bangalore Rajeeva, Tianyu Yuan, Zi-Hao Guo, Yen-Hao Lin, Mohammed Al-Hashimi, Yuebing Zheng and Lei Fang
DOI: 10.1039/C5SC02385H, Edge Article

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In the congested intracellular environment, scientists in the Netherlands and the US have found a way for molecules to manoeuvre through the crowds and arrive at their destination faster, increasing the efficiency of lengthy laboratory processes, such as polymerase chain reactions (PCRs).

Biomolecules must find and associate with other biomolecules to carry out basic processes within a cell. To do so, many will randomly diffuse within the cell’s three-dimensional space, which is very time-consuming. Some proteins have evolved to glide along DNA and sample positions in a one-dimensional fashion in search of their target, akin to driving down a highway and stopping to sightsee along the way. This has the potential to speed up these processes. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access and free to read:
Speeding up biomolecular interactions by molecular sledding
Alexander Turkin, Lei Zhang, Alessio Marcozzi, Walter F. Mangel, Andreas Herrmann and Antoine M. van Oijen
DOI: 10.1039/C5SC03063C, Edge Article

Eucalyptus bears both catalyst and biofuel
by Elisabeth Ratcliffe 

Leftovers from the catalytic conversion of biomass into biofuels and biochemicals need not go to waste. So say Japanese researchers who have devised a method using eucalyptus trees that regenerates residue from the process into fresh catalyst. Read the full  article in Chemistry World» 

Read the original journal article in Chemical Science:
Hydrolysis of woody biomass by a biomass-derived reusable heterogeneous catalyst
Hirokazu Kobayashi, Hiroyuki Kaiki, Abhijit Shrotri, Kota Techikawara and Atsushi Fukuoka
DOI: 10.1039/C5SC03377B, Edge Article 

Add more peroxide to stabilise new drug molecules
by Michaela Muehlberg 

Scientists in the US and Russia have performed theoretical calculations to better understand the well-known instability of peroxides as well as the astonishing higher stability of bis- and tris-peroxides. For the latter, they found that multiple O–O bonds appear to exert a stabilising stereoelectronic effect on each other, which boosts stability. Read the full article in Chemistry World» 

Read the original journal article in Chemical Science:
Stereoelectronic source of the anomalous stability of bis-peroxides
Gabriel dos Passos Gomes, Vera Vil’, Alexander Terent’ev and Igor V. Alabugin
DOI: 10.1039/C5SC02402A, Edge Article

Gold cluster bends between two isomers
by Sage Bowser

Collaborating research groups in the US and China have observed a rare type of isomerism in a gas phase Au2I3– cluster. The cluster exhibits two stable structures with the same electronic configuration and potential energy surface that vary in only their Au–I–Au bond angles, a phenomenon that the researchers have dubbed ‘bond-bending isomerism’. Read the full article in Chemistry World» 

Read the original journal article in Chemical Science:
Bond-bending isomerism of Au₂I₃⁻: competition between covalent bonding and aurophilicity
Wan-Lu Li, Hong-Tao Liu, Tian Jian, Gary V. Lopez, Zachary A. Piazza, Dao-Ling Huang, Teng-Teng Chen, Jing Su, Ping Yang, Xin Chen, Lai-Sheng Wang and Jun Li
DOI: 10.1039/C5SC03568F, Edge Article

As children, we learn very early on about the concept of shape and size complementarity. No matter how many times you try, the square peg doesn’t fit in the round hole, and that second (or third!) piece of cake just wasn’t a good idea. This same concept also extends to supramolecular interactions, especially when we consider the arena of host–guest chemistry.

Generally speaking, the conformation of a macrocyclic host is relatively rigid, which means that the scope of host molecules it can encase is also somewhat limited. Whilst this feature of host–guest chemistry and molecular recognition is the basis for a range of catalytic events and the template-directed synthesis of mechanically interlocked molecules, it would be advantageous in expanding the scope of this field if a macrocycle existed that could happily host a wide range of guest molecules.

Wei Jiang and his team from the South University of Science and Technology of China have achieved this feat in the synthesis of a naphthalene-based macrocycle, oxatub[4]arene, that has the rigidity required of host–guest interactions, but, in addition, the flexibility necessary to adapt to and accommodate the chemical shape and size of a variety of guest molecules. Its naphthalene units are able to rotate, and in doing so generate four predominant conformers, each with different cavity depths and diameters, as well as different binding affinities for molecular guest molecules.

The dynamic nature of this unique macrocycle is an important step forward in the construction of host–guest complexes, especially as we look to introduce further complexity into the arsenal of supramolecular interactions we have at our disposal, and particularly in the development of increasingly multifaceted stimuli-responsive and molecular machines.

Read this hot ChemSci article in full – it’s open access and free to download:

Oxatub[4]arene: A smart macrocyclic receptor with multiple interconvertible cavities
Fei Jia, Zhenfeng He, Liu-Pan Yang, Zhi-Sheng Pan, Min Yi, Ren-Wang Jiang and Wei Jiang
Chem. Sci., 2015, Advance Article.
DOI: 10.1039/C5SC03251B, Edge Article

About the Writer:

Anthea Blackburn is a guest web writer for Chemical Science. Anthea is a recent graduate student hailing from New Zealand. She studied at Northwestern University in the US under the tutelage of Prof. Fraser Stoddart (a Scot), where she exploited supramolecular chemistry to develop multidimensional systems and study the emergent properties that arise in these superstructures. When time and money allowed, she ambitiously attempted to visit all 50 US states.

Take a look at this selection of recently published referee-recommended articles – all are open access and free to download.

Connecting electrodes with light: one wire, many electrodes
Moinul H. Choudhury, Simone Ciampi, Ying Yang, Roya Tavallaie, Ying Zhu, Leila Zarei, Vinicius R. Gonçales and J. Justin Gooding
DOI: 10.1039/C5SC03011K, Edge Article

Linear scaling relationships and volcano plots in homogeneous catalysis – revisiting the Suzuki reaction
Michael Busch, Matthew D. Wodrich and Clémence Corminboeuf
DOI: 10.1039/C5SC02910D, Edge Article

IspH–RPS1 and IspH–UbiA: “Rosetta stone” proteins
Guodong Rao, Bing O’Dowd, Jikun Li, Ke Wang and Eric Oldfield
DOI: 10.1039/C5SC02600H, Edge Article

An optoelectronic nose for identification of explosives
Jon R. Askim, Zheng Li, Maria K. LaGasse, Jaqueline M. Rankin and Kenneth S. Suslick
DOI: 10.1039/C5SC02632F, Edge Article

A portable optoelectronic device for accurately detecting a wide array of explosives has been reported in a recently published Chemical Science article.

Kenneth Suslick and co-workers from the University of Illinois at Urbana-Champaign, USA, have combined responsive dyes to differentiate between explosive compound groups with sensitivity up to ten times that of currently used methods.

This detection kit was able to distinguish:

• common explosives
• compounds related to home-made explosives
• compounds found in improvised explosive devices
• signature non-explosive compounds found in military-grade explosives

Integration of the colorimetric array with a hand-held reader based on business card scanners means there is no need for specialist expertise by the user. Its fast scan rates, portability and lack of moving parts could find use in accompanying existing security technology.

Read the original article in Chemical Science – it’s open access:

An optoelectronic nose for identification of explosives
Jon R. Askim, Zheng Li, Maria K. LaGasse, Jaqueline M. Rankin and Kenneth S. Suslick
DOI: 10.1039/C5SC02632F, Edge Article
Open Access

Using theoretical calculations, researchers in the US and Japan, have cast a spotlight on the vital role that subtle, and previously overlooked, dispersion forces play in stabilising p-block heavy element bonding.

It was once thought that heavy elements could not form multiple bonds, but landmark work by inorganic chemists such as Mike Lappert in the 1970s blew the doors off this notion and opened up a whole new world for main group chemistry. Since then, the study of heavier p-block elements with multiple bonds has remained a topic of broad interest and exciting discoveries. One key development was that sterically large ligands block decomposition and stabilise bonds. However, questions over how and why these compounds remain stable continue to be debated. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access:
The multiple bonding in heavier group 14 element alkene analogues is stabilized mainly by dispersion force effects
Jing-Dong Guo, David J. Liptrot, Shigeru Nagase and Philip P. Power 
DOI: 10.1039/C5SC02707A, Edge Article

Durrant has proposed a simple but quantitative measure of hypervalency

A researcher in the UK has presented a controversial new definition for hypervalency that may ignite debates over atomic charge and allow students to draw nitrogen atoms with five covalent bonds.

Marcus Durrant from the University of Northumbria describes his account of hypervalency as going back to the drawing board. By bringing together electron counts on atoms in different resonance structures, he presents a valence electron equivalent parameter to indicate an overall number of electrons associated with each atom. A count greater than eight defines hypervalency. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access:
A quantitative definition of hypervalency
Marcus C. Durrant 
DOI: 10.1039/C5SC02076J, Edge Article

Here are some of the latest referee-recommended articles published in Chemical Science – all are open access and free to read:

Design rationale of thermally responsive microgel particle films that reversibly absorb large amounts of CO2: fine tuning the pKa of ammonium ions in the particles
Mengchen Yue, Yu Hoshino and Yoshiko Miura 
DOI: 10.1039/C5SC01978H, Edge Article

Singly and doubly ß-to-ß platinum-bridged porphyrin dimers and their reductive eliminations
Hua-Wei Jiang, Takayuki Tanaka and Atsuhiro Osuka 
DOI: 10.1039/C5SC02553B, Edge Article

Fluorescent carbon dot–molecular salt hydrogels
Angelina Cayuela, Stuart R. Kennedy, M. Laura Soriano, Christopher D. Jones, Miguel Valcárcel and Jonathan W. Steed 
DOI: 10.1039/C5SC01859E, Edge Article

Molecular computing: paths to chemical Turing machines
Shaji Varghese, Johannes A. A. W. Elemans, Alan E. Rowan and Roeland J. M. Nolte 
DOI: 10.1039/C5SC02317C, Perspective

Lab on a single microbead: an ultrasensitive detection strategy enabling microRNA analysis at the single-molecule level
Xiaobo Zhang, Chenghui Liu, Lingbo Sun, Xinrui Duan and Zhengping Li 
DOI: 10.1039/C5SC02641E, Edge Article

An elegant strategy for detecting minuscule quantities of microRNA using just a single functionalised microbead could be an important innovation for biomedical research and molecular diagnostics.

Identifying biomolecules with vanishingly small copy numbers in cells is vital in deciphering the chemical blueprint for life. Homogeneous exponential amplification methods (such as the polymerase chain reaction), northern blotting, microarray detection and the isothermal exponential amplification reaction (EXPAR) are just some of the techniques that have undergone extensive tailoring to detect all manner of genetic material in cells as sensitively as possible. However, few approaches have even come close to reliably detecting nucleic acids at the single molecule level. Read the full article in Chemistry World»

Read the original journal article in Chemical Science – it’s open access:
Lab on a single microbead: an ultrasensitive detection strategy enabling microRNA analysis at the single-molecule level
Xiaobo Zhang, Chenghui Liu, Lingbo Sun, Xinrui Duan and Zhengping Li 
Chem. Sci., 2015, Advance Article
DOI: 10.1039/C5SC02641E, Edge Article