Supramolecular chirality and reversible chiroptical switching in new chiral liquid-crystal azopolymers

The synthesis of chiral liquid-crystalline polymers of well-controlled structure (linear and three-armed star-shaped) with distinct average chain lengths and low polydispersity was achieved by atom transfer radical polymerisation (ATRP) of a new optically active monomer (S)-4-[6-(2-methacryloyloxypropanoyloxy)hexyloxy)]-4'-ethoxyazobenzene [(S)-ML6A], containing the L-lactic residue of one absolute configuration in the side-chain. All the obtained polymeric samples, characterised by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and polarised optical microscopy (POM), exhibit a smectic A(1/2) (fully interdigitated) liquid-crystalline phase and high cleaning points, with transition temperatures dependent on the average polymerisation degree and the macromolecular structure. The chirality originated at the molecular level by the asymmetric functionality of the L-lactic acid residue provides the polymers, in the smectic phase, of highly homogeneous conformations with a prevailing chirality related to the presence of H-aggregates having conformational dissymmetry of one prevailing screw-sense. By irradiating with circularly polarised light (CPL), it is possible to photomodulate the chiroptical properties of these intrinsically chiral polymeric thin films. Upon irradiation with left-handed CPL (l-CPL), the circular dichroism (CD) spectra of the films show enhancement of ellipticity and a net inversion of sign. The effect is reversible and the mirror image of the CD spectrum can be restored by pumping with right-handed CPL radiation (r-CPL). The results show the ability of l-CPL to invert the supramolecular chirality of the materials and demonstrate the essential role of azoaromatic aggregates.     

Influence of ions on the structural organization of dipolar liquids probed by the noncoincidence effect: experimental and quantum chemical results

The C=O stretching [nu(C=O)] Raman bands of the carbonyl solvents, S (acetone and acetophenone), in some electrolytic solutions of lithium and sodium salts (M(+)X(-)) are analyzed. The large and negative values of the noncoincidence effect (NCE=nu(ani)-nu(iso)) measured for the component of this band generated by the solvent-ion interactions are interpreted in the light of the results of ab initio quantum chemical calculations performed for clusters of type (S)nM(+) and also on the basis of the transition dipole coupling mechanism between pairs of nu(C=O) oscillators. The effects of the size of the ion M(+) and of the solvation number n on the NCE are analyzed. It is shown that the decrease of the NCE resulting from the change in the size of the ion M(+) from Li(+) to Na(+) is appreciably counterbalanced by the increase of the NCE arising form the change in the ion solvation number n from 4 for Li(+) to 6 for Na(+).     

Metabolically Active,Fully Hydrolysable Polymersomes

The synthesis and aqueous self‐assembly of a new class of amphiphilic aliphatic polyesters are presented. These AB block polyesters comprise polycaprolactone (hydrophobe) and an alternating polyester from succinic acid and an ether‐substituted epoxide (hydrophile). They self‐assemble into biodegradable polymersomes capable of entering cells. Their degradation products are bioactive, giving rise to differentiated cellular responses inducing stromal cell proliferation and macrophage apoptosis. Both effects emerge only when the copolymers enter cells as polymersomes and their magnitudes are size dependent.     

The photoreactions of simple amides with NO. Gaining insight into radical bio-damages through an EPR case study

Eight simple amides have been subjected to UV irradiation in the presence of either MNP or NO. In all cases radical species were generated: these were detected by means of EPR spectroscopy in the form of different nitroxides resulting from the trapping of the primary radicals. NO acted as a double spin trap, scavenging a radical to afford a diamagnetic nitroso derivative that in turn acted as trap towards another radical unit. As amido-groups are present in components of skin tissue and may be present in many therapeutic or cosmetic products used as skin sunscreen, and NO is a ubiquitous endogenous reactive species, the nitroxides detected in the present studies might participate in radical processes triggered by sun exposure and resulting in damages, even severe, of biological tissues.     

Molecular associations of [2.2]paracyclophanearylhydrazones with organic acceptors,VIII

Summary Molecular complexes of mono and disubstituted [2.2]paracyclophanehydrazones with organic acceptors have been studied by means of thermodynamic and spectroscopic properties. Furthermore, the enhancement of the donor strength, induced by the hydrazono group, is viewed in the light of substituent as well as transannular effects.

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Molekulare Assoziation von [2.2]Paracyclophanarylhydrazonen mit organischen Akzeptoren, 8. Mitt.

Zusammenfassung Es wurden Molekülkomplexe von mono- und disubstituierten [2.2]Paracyclophanarylhydrazonen mit organischen Akzeptoren mittels thermodynamischer und spektroskopischer Methoden untersucht. Zusätzlich wird der Anstieg in der Donorstärke, der von der Hydrazonogruppe induziert wird, im Hinblick auf Substituenten- und auch transannulare Effekte diskutiert.

     

Crude extract of Origanum vulgare L. induced cell death and suppressed MAPK and PI3/Akt signaling pathways in SW13 and H295R cell lines

Oregano (Origanum vulgare L.) is a common aromatic plant used in Mediterranean and Asian Regions for treating respiratory diseases, painful menstruation, rheumatoid arthritis, etc. Recently its role as an anticancer plant has been suggested, although oregano has been never evaluated into adrenocortical tumour cell models. This study analysed for the first time the anticancer effects of a crude extract of wild mountain oregano (Origanum vulgare L.) in SW13 and H295R cell lines. The crude extract was characterised by GC/MS and the toxic effects of oregano were first analysed by brine shrimp lethality assay. Our findings demonstrated that oregano decreased cell viability, survival, modified cell cycle and induced cell death (through necrotic process) and that the effects can be attributed to a blockade of MAPK and PI3 K/Akt pathways. These results suggest that oregano extract exerts anticancer activities in adrenocortical tumour cell lines, providing evidence for further research in higher models.     

Spray-drying as a tool to disperse conductive carbon inside Na<Subscript>2</Subscript>FePO<Subscript>4</Subscript>F particles by addition of carbon black or carbon nanotubes to the precursor solution

In this work, Na₂FePO₄F-carbon composite powders were prepared by spray-drying a solution of inorganic precursors with 10 and 20 wt% added carbon black (CB) or carbon nanotubes (CNTs). In order to compare the effect of CB and CNT when added to the precursor solutions, the structural, electrochemical, and morphological properties of the synthesized Na₂FePO₄F-xCB and Na₂FePO₄F-xCNT samples were systematically investigated. In both cases, X-ray diffraction shows that calcination at 600 °C in argon leads to the formation of Na₂FePO₄F as the major inorganic phase. ⁵⁷Fe Mössbauer spectroscopy was used as complementary technique to probe the oxidation states, local environment, and identify the composition of the iron-containing phases. The electrochemical performance is markedly better in the case of Na₂FePO₄F-CNT (20 wt%), with specific capacities of about 100 mAh/g (Na₂FePO₄F-CNT) at C/4 rate vs. 50 mAh/g for Na₂FePO₄F-CB (20 wt%). SEM characterization of Na₂FePO₄F-CB particles revealed different particle morphologies for the Na₂FePO₄F-CNT and Na₂FePO₄F-CB powders. The carbon-poor surface observed for Na₂FePO₄F-CB could be due to a slow diffusion of carbon in the droplets during drying. On the contrary, Na₂FePO₄F-CNT shows a better CNT dispersion inside and at the surface of the NFPF particles that improves the electrochemical performance.     

Results of the search for strange quark matter and Q-balls with the SLIM experiment

The SLIM experiment at the Chacaltaya high altitude laboratory was sensitive to nuclearites and Q-balls which could be present in the cosmic radiation as possible Dark Matter components. It was sensitive also to strangelets, i.e. small lumps of Strange Quark Matter predicted at such altitudes by various phenomenological models. The analysis of 427 m² of Nuclear Track Detectors exposed for 4.22 years showed no candidate event. New upper limits on the flux of downgoing nuclearites and Q-balls at the 90% C.L. were established. The null result also restricts models for strangelets propagation through the Earth atmosphere.     

Quasi-one-dimensional Bose gases with a large scattering length

Bose gases confined in highly elongated harmonic traps are investigated over a wide range of interaction strengths using quantum Monte Carlo techniques. We find that the properties of a Bose gas under tight transverse confinement are well reproduced by a 1D model Hamiltonian with contact interactions. We point out the existence of a unitary regime, where the properties of the quasi-1D Bose gas become independent of the actual value of the 3D scattering length a(3D). In this unitary regime, the energy of the system is well described by a hard-rod equation of state. We investigate the stability of quasi-1D Bose gases with positive and negative a(3D).