Tetraalkynyl calix[4]arenes with advanced NLO properties

Rigid, highly conjugated tetraalkynyl-calix[4]arenes synthesised via Sonogashira coupling give rise to improved second-order hyperpolarizability values as determined by hyper-Rayleigh scattering--a technique that in addition to X-ray crystallography also allows for the conformational analysis of the calixarene structures in solution.     

Mesophase behaviour and thermal stability of octa-alkoxy substituted phthalocyaninatocobalt (II) complexes

Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C₄H₉O) and n-octadecyloxy (C₁₈H₃₇O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Col_h). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C₁₃H₂₇O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry.     

Suppression of noise in a noisy optical trap

We have experimentally explored and clarified the concept of noise suppression in intrinsically noisy systems by adding noise at the input using a microscopic bead held in a moving and intensity-modulated optical trap. By coupling the stiffness of the optical trap to its position, we have explicitly constructed an experimental model system in which added fluctuations in the trap position result in reduced variance of the observed bead position as compared to a stationary trap. This reduction in variance and the spectral properties of the observed output noise agree with theoretical predictions. Our experiment demonstrates that the essential aspect of noise reduction in such a system is that the added fluctuations drive the system into states with a reduced intensity of intrinsic noise sufficiently often.     

Influence of fullerene photodimerization on the PCBM crystallization in polymer: Fullerene bulk heterojunctions under thermal stress

For an increased lifetime of polymer:fullerene bulk heterojunction (BHJ) solar cells, an understanding of the chemical and morphological degradation phenomena taking place under operational conditions is crucial. Phase separation between polymer and fullerene induced by thermal stress has been pointed out as a major issue to overcome. While often the effect of thermal stress on the morphology of polymer:fullerene BHJ is investigated in the darkness, here we observe that light exposure slows down fullerene crystallization and phase separation induced at elevated temperatures. The observed photo‐stabilizing effect on active layer morphology is quite independent on the polymer and is attributed to light‐induced dimerization of the fullerene. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1209–1214     

Indefinite Kasparov Modules and Pseudo-Riemannian Manifolds

We present a definition of indefinite Kasparov modules, a generalisation of unbounded Kasparov modules modelling non-symmetric and non-elliptic (e.g. hyperbolic) operators. Our main theorem shows that to each indefinite Kasparov module we can associate a pair of (genuine) Kasparov modules, and that this process is reversible. We present three examples of our framework: the Dirac operator on a pseudo-Riemannian spin manifold (i.e. a manifold with an indefinite metric); the harmonic oscillator; and the construction via the Kasparov product of an indefinite spectral triple from a family of spectral triples. This last construction corresponds to a foliation of a globally hyperbolic spacetime by spacelike hypersurfaces.     

Photochromism Emergence in N‐Salicylidene p‐Aminobenzenesulfonate Diallylammonium Salts

N‐Salicylidene p‐aminobenzenesulfonate salts were prepared by in situ condensation of p‐aminobenzenesulfonate diallylammonium salt and salicylaldehyde. Modulation of thermo‐ and photochromism was achieved by varying the alkyl chain length of the diallylammonium counter‐cation. A structural–optical properties investigation reveals that both crystal packing and dihedral angle between aromatic rings of the N‐salicylidene aniline switch are not sufficient to predict the occurrence of photochromism in the solid state. The available free space around the N‐salicylidene p‐aminobenzenesulfonate, in addition to the flexibility of the nearby environment, is shown to be of major importance for the cis→trans isomerisation to occur as well as for the stabilisation of the trans‐keto form. Emergence of photochromic properties was determined from the diallylhexylammonium cation within the series of investigated counter‐cations. High stability is observed for the trans‐keto form of one polymorph of N‐salicylidene p‐aminobenzenesulfonate diallylhexylammonium salt (k=2.4×10^?7 s^?1).     

Modelling of Unsteady Transition in Low-Pressure Turbine Blade Flows with Two Dynamic Intermittency Equations

A transition model for describing wake-induced transition is presented based on the SST turbulence model by Menter and two dynamic equations for intermittency: one for near-wall intermittency and one for free-stream intermittency. In the Navier-Stokes equations, the total intermittency factor, which is the sum of the two, multiplies the turbulent viscosity computed by the turbulence model. The quality of the transition model is illustrated on the T106A test cascade for two Reynolds numbers, using experimental results by Stieger and Hodson for transition mainly due to kinematic wake impact on a separation bubble. The quality of the model is also revealed on the T106D test cascade using experimental results from Hilgenfeld, Stadtmuller and Fottner for wake turbulence induced transition. The test cases differ in pitch to chord ratio, Reynolds number and inlet free-stream turbulence intensity, causing different transition mechanisms. The unsteady results are presented in space-time diagrams of shape factor and wall shear stress on the suction side. The results show the capability of the model to capture the physics of unsteady transition in separated state. Inevitable shortcomings are revealed as well.