Laser nanosources based on planar photonic crystals as new platforms for nanophotonic devices

Two-dimensional photonic crystal lasers have been fabricated on III–V semiconductor slabs. Tuning of the spontaneous emission in micro and nanocavities has been achieved by accurate control of the slab thickness. Different structures, some of them of new application to photonic crystal lasers, have been fabricated like the Suzuki-phase or the coupled-cavity ring-like resonators. Laser emission has been obtained by pulsed optical pumping. Optical characterization of the lasing modes have been performed showing one or more laser peaks centred around 1.55 μm. Far field characterization of the emission pattern has been realized showing different patterns depending on the geometrical shape of the structures. These kinds of devices may be used as efficient nanolaser sources for optical communications or optical sensors.     

Ab initio X-ray powder diffraction characterisation of molecule-based magnetic materials

Use of ab initio X-ray powder diffraction (XRPD) methods in the study of magnetically active species of covalent nature is presented. Selected cases are chosen in order to underline the power of XRPD methodologies, highlighting the importance of independent physico-chemical information from ancillary techniques.     

2H NMR spectra of 2-(p-heptylbenzoyloxy)-5-(p-heptylbenzenazo)tropone. A new sigmatropic liquid crystal

Liquid crystals incorporating in their molecular framework a seven-membered ring are still relatively rare [1]. Recently the synthesis and thermal behaviour of a series of liquid crystal materials having a tropone moiety in their mesogenic core have been reported [2-4]. These mesogens, based on a 2-(acyloxy)tropone core structure, show intramolecular migration of the acyl substituents between the two oxygen atoms at C-1 and C-2, an effect already known for simple 2-(acyloxy)tropones in their isotropic solutions [5]. This migration involves a concerted [1, 9]-sigmatropic rearrangement [2]. This rearrangement could play a major role in determining the properties of the mesophases: it has been suggested in fact that, because of this rearrangement, the mesogenic molecules acquire a mean rod-like shape which can sustain the mesophase formation [2].     

Phase separation of p53 precedes aggregation and is affected by oncogenic mutations and ligands

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF). The mechanism of the formation of the aggregates in the nucleus remains uncertain. The present study demonstrated that the DNA-binding domain of p53 (p53C) underwent phase separation (PS) on the pathway to aggregation under various conditions. p53C phase separated in the presence of the crowding agent polyethylene glycol (PEG). Similarly, mutant p53C (M237I and R249S) underwent PS; however, the process evolved to a solid-like phase transition faster than that in the case of wild-type p53C. The data obtained by microscopy of live cells indicated that transfection of mutant full-length p53 into the cells tended to result in PS and phase transition (PT) in the nuclear compartments, which are likely the cause of the GoF effects. Fluorescence recovery after photobleaching (FRAP) experiments revealed liquid characteristics of the condensates in the nucleus. Mutant p53 tended to undergo gel- and solid-like phase transitions in the nucleus and in nuclear bodies demonstrated by slow and incomplete recovery of fluorescence after photobleaching. Polyanions, such as heparin and RNA, were able to modulate PS and PT in vitro. Heparin apparently stabilized the condensates in a gel-like state, and RNA apparently induced a solid-like state of the protein even in the absence of PEG. Conditions that destabilize p53C into a molten globule conformation also produced liquid droplets in the absence of crowding. The disordered transactivation domain (TAD) modulated both phase separation and amyloid aggregation. In summary, our data provide mechanistic insight into the formation of p53 condensates and conditions that may result in the formation of aggregated structures, such as mutant amyloid oligomers, in cancer. The pathway of mutant p53 from liquid droplets to gel-like and solid-like (amyloid) species may be a suitable target for anticancer therapy.

Mutant p53 tends to form aggregates with amyloid properties, especially amyloid oligomers inside the nucleus, which are believed to cause oncogenic gain-of-function (GoF).     

2-(2-Hydroxyaryl)cinnamic amides: a new class of axially chiral molecules

The syntheses of several differently substituted amides formally derived from a chiral amine, either E-2-(2-hydroxyphenyl)cinnamic acid or both E- and Z-2-(2-hydroxynaphthyl)cinnamic acid, are reported. These molecules display a restricted rotation about the C₂-C_aryl bond. The barriers to rotation about the C₂-C_aryl bond were measured by the dynamic ¹H NMR and were found to vary between 11.8 and 24.5 kcal mol⁻¹, depending on the substitution. In particular, E-2-(2-hydroxynapthyl)cinnamic amides, displayed a high barrier to rotation (ΔG_c^‡=24.4 kcal mol⁻¹) and could be isolated in both diastereomerically pure forms at room temperature. The X-ray structure of one E-2-(2-hydroxynapthyl)cinnamic amide, was resolved, enabling for the determination of the absolute configuration of the chiral axis (aR).     

Optically activated functionalization reactions in Si quantum dots

Using ab initio calculations, we have studied the influence of optical activation on functionalization reactions of silicon quantum dots with unsaturated hydrocarbons. We find that the energy barrier for the replacement of silicon-hydrogen with silicon-carbon bonds is dramatically reduced if the silicon dot is optically excited. These results provide an explanation for recent experiments on optically excited porous silicon. In addition, our calculations point at the existence of an intermediate spin-polarized state formed by the dot and an alkene or alkyne, upon relaxation after absorbing a photon. This state could be detected experimentally, by, for example, electron spin resonance measurements. Based on the results of our calculations as a function of the dot size, varied from 0.8 to 1.5 nm, we propose that light activated reactions could be used to functionalize and size select silicon quantum dots at the same time.