Nanostructure and dielectric properties of a twist-bend nematic liquid crystal mixture

We present freeze-fracture transmission electron microscopy (FF-TEM), dielectric spectroscopy and electro-optic measurements on a dimeric liquid crystal mixture, which previously was proposed to form the twist-bend nematic (N_tb) phase. Our FF-TEM studies provide a direct image of a 10.5 nm periodic structure, consistent with the expected nanoscale, heliconical twist-bend modulation of the molecular orientation. Dielectric measurements in the 100 Hz to 10 MHz range reveal three nearly Debye-type dispersion processes in the nematic and the twist-bend phase. Low frequency 8 V/µm electric fields applied on planar cells cause the optical-scale stripe texture (another characteristic feature of the N_tb phase) to disappear. Higher (>16 V/µm) fields gradually realign the heliconical axis along the electric field; it relaxes back after the field removal.     

The effect of a suppressor to environmental noise – A case study

The purpose of the study is to describe the effect of a suppressor to environmental noise with a typical Finnish rifle shooting range that has a shooting shelter and some noise berms. The noise measurements were carried out at Kyronpelto shooting range situated near Mikkeli in Finland. The range is equipped with wooden shooting shelter, the shooting distance is 150 m, and it has berms on sides and at the impact end. The terrain is relatively flat in the area. The best noise area reduction caused by a suppressor could be seen at angles of 315–45° from the shooting direction. The projectile noise dominates at angles 45–70°, and the effect of the suppressor is very small. To the side and back the shooting shelter has already gained significant noise attenuation, and therefore the suppressor cannot reduce the noise area much more. When there was a relatively tight shooting shelter to the side and back, the suppressor did not reduce the environmental noise area significantly any more. It can be calculated that the noise area of 65 dB (L_AImax) is reduced from 95 ha to 50 ha (0.95 km²–0.50 km²) with the help of a suppressor. However, most of the area is situated to the shooting sector and it has to be unoccupied for safety reasons.     

Adsorbate conformation determines catalytic chemoselectivity: crotonaldehyde on the Pt(111) surface

Molecular orientation, which depends on surface coverage, determines whether or not catalytic hydrogenation is chemoselective.     

Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}

The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.     

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Highly Charged Ruthenium(II) Polypyridyl Complexes as Effective Photosensitizer in Photodynamic Therapy

A comparative study between two novel, highly water soluble, ruthenium(II) polypyridyl complexes, [Ru(phen)₂ L ′] and [Ru(phen)₂Cu(II) L ′] ( L and L -Cu^II), containing the polyaazamacrocyclic unit 4,4′-(2,5,8,11,14-pentaaza[15])-2,2′-bipyridilophane ( L ′), is herein reported. L and L -Cu^II interact with calf-thymus DNA and efficiently cleave DNA plasmid when light-activated. They also possess great penetration abilities and photo-induced biological activities, evaluated on an A375 human melanoma cell line, with L -Cu^II being the most effective. Our study highlights the key role of the Fenton active Cu^II center within the macrocycle framework, that would play a synergistic role with light activation in the formation of cytotoxic ROS species. Based on these results, an optimal design of Ru^II polypyridyl systems featuring specific Cu^II-chelating polyamine units could represent a suitable strategy for the development of novel and effective photosensitizers in photodynamic therapy.