Flat corannulene: when a transition state becomes a stable molecule

Flat corannulene has been considered so far only as a transition state of the bowl-to-bowl inversion process. This study was driven by the prediction that substituents with strong steric repulsion could destabilize the bowl-shaped conformation of this molecule to such an extent that the highly unstable planar geometry would become an isolable molecule. To examine the substituents'' effect on the corannulene bowl depth, optimized structures for the highly-congested decakis(t-butylsulfido)corannulene were calculated. The computations, performed with both the M06-2X/def2-TZVP and the B3LYP/def2-TZVP methods (the latter with and without Grimme''s D3 dispersion correction), predict that this molecule can achieve two minimum structures: a flat carbon framework and a bowl-shaped structure, which are very close in energy. This rather unusual compound was easily synthesized from decachlorocorannulene under mild reaction conditions, and X-ray crystallographic studies gave similar results to the theoretical predictions. This compound crystallized in two different polymorphs, one exhibiting a completely flat corannulene core and the other having a bowl-shaped conformation.

The first flat metal-free corannulene derivative was predicted by computations and achieved by synthesis.     

Dual‐Functional Semithiobambusurils

Semithiobambusurils, which represent a new family of macrocyclic host molecules, have been prepared by a convenient, scalable synthesis. These new cavitands are double functional: they strongly bind a broad variety of anions in their interiors and metal ions at their sulfur‐edged portals. The solid‐state structure of semithiobambus[4]uril with HgCl₂ demonstrates the ability of these compounds to form linear chains of coordination polymers with thiophillic metal ions. The crystal structure of semithiobambus[6]uril with tetraphenylphosphonium bromide exhibits the unique anion‐binding properties of the host cavity and the characteristics of the binding site.     

Evidence for a near-resonant charge transfer mechanism for double-stranded peptide nucleic acid

We present evidence for a near-resonant mechanism of charge transfer in short peptide nucleic acid (PNA) duplexes obtained through electrochemical, STM break junction (STM-BJ), and computational studies. A seven base pair (7-bp) PNA duplex with the sequence (TA)(3)-(XY)-(TA)(3) was studied, in which XY is a complementary nucleobase pair. The experiments showed that the heterogeneous charge transfer rate constant (k(0)) and the single-molecule conductance (σ) correlate with the oxidation potential of the purine base in the XY base pair. The electrochemical measurements showed that the enhancement of k(0) is independent, within experimental error, of which of the two PNA strands contains the purine base of the XY base pair. 7-bp PNA duplexes with one or two GC base pairs had similar measured k(0) and conductance values. While a simple superexchange model, previously used to rationalize charge transfer in single stranded PNA (Paul et al. J. Am. Chem. Soc. 2009, 131, 6498-6507), describes some of the experimental observations, the model does not explain the absence of an enhancement in the experimental k(0) and σ upon increasing the G content in the duplexes from one to two. Moreover, the superexchange model is not consistent with other studies (Paul et al. J. Phys. Chem. B 2010, 114, 14140), that showed a hopping charge transport mechanism is likely important for PNA duplexes longer than seven base pairs. A quantitative computational analysis shows that a near-resonant charge transfer regime, wherein a mix of superexchange and hopping mechanisms are expected to coexist, can rationalize all of the experimental results.     

Repulsive interaction can be a key design element of molecular rotary motors

Low-barrier molecular rotary motors having rotaxane architecture can be constructed using a cucurbituril host and a polyyne guest serving as stator and rotator, respectively. The repulsive interaction between these components is supported by molecular mechanics calculations with model systems and experimentally verified by X-ray crystallography with several synthetic host-guest complexes, all suggesting that the diyne rod floats at the center of the macrocyclic host with no apparent van der Waals contacts between them. Further support for these interactions is suggested by microcalorimetry measurements.     

Computational design, synthesis and biological evaluation of para-quinone-based inhibitors for redox regulation of the dual-specificity phosphatase Cdc25B

Quinoid inhibitors of Cdc25B were designed based on the Linear Combination of Atomic Potentials (LCAP) methodology. In contrast to a published hypothesis, the biological activities and hydrogen peroxide generation in reducing media of three synthetic models did not correlate with the quinone half-wave potential, E(1/2).     

Angular dependence of the magnetic-field driven superconductor-insulator transition in thin films of amorphous indium-oxide

A significant anisotropy of the magnetic-field driven superconductor-insulator transition is observed in thin films of amorphous indium-oxide. The anisotropy is largest for more disordered films which have a lower transition field. At higher magnetic fields the anisotropy reduces and even changes sign beyond a sample specific and temperature independent magnetic field value. The data are consistent with the existence of more than one mechanism affecting transport at high magnetic fields.     

On the Lamb vector and the hydrodynamic charge

This work is an attempt to test the concept of the hydrodynamic charge (analogous to the electric charge in electromagnetism) in the simple case of a coherent structure such as the Burgers vortex. We provide experimental measurements of both the so-called Lamb vector and its divergence (the charge) by two-dimensional particles images velocimetry. In addition, we perform a Helmholtz–Hodge decomposition of the Lamb vector in order to explore its topological features. We compare the charge with the well-known Q-criterion in order to assess its interest in detecting and characterizing coherent structure. Usefulness of this concept in studies of vortex dynamics is demonstrated.

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