Isotropic-Nematic Transition in Liquid-Crystalline Elastomers

In liquid-crystalline elastomers, the nematic order parameter and the induced strain vary smoothly across the isotropic-nematic transition, without the expected first-order discontinuity. To investigate this smooth variation, we measure the strain as a function of temperature over a range of applied stress, for elastomers crosslinked in the nematic and isotropic phases, and analyze the results using a variation on Landau theory. This analysis shows that the smooth variation arises from quenched disorder in the elastomer, combined with the effects of applied stress and internal stress.Comment: 4 pages, including 4 postscript figures, uses REVTeX

Competing dynamics of intramolecular deactivation and bimolecular charge transfer processes in luminescent Fe( iii ) N-heterocyclic carbene complexes

Steady state and ultrafast spectroscopy on [Fe$^{III}$(phtmeimb)$_{2}$]PF$_{6}$ (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate) was performed over a broad range of temperatures. The intramolecular deactivation dynamics of the luminescent doublet ligand-to-metal charge-transfer ($^{2}$LMCT) state was established based on Arrhenius analysis, indicating the direct deactivation of the $^{2}$LMCT state to the doublet ground state as a key limitation to the lifetime. In selected solvent environments photoinduced disproportionation generating short-lived Fe(IV) and Fe(II) complex pairs that subsequently undergo bimolecular recombination was observed. The forward charge separation process is found to be temperature-independent with a rate of ∼1 ps$^{–1}$. Subsequent charge recombination takes place in the inverted Marcus region with an effective barrier of 60 meV (483 cm$^{–1}$). Overall, the photoinduced intermolecular charge separation efficiently outcompetes the intramolecular deactivation over a broad range of temperatures, highlighting the potential of [Fe$^{III}$(phtmeimb)$_{2}$]PF$_{6}$ to perform photocatalytic bimolecular reactions

Carbene based photochemical molecular assemblies for solar driven hydrogen generation

Novel photocatalysts based on ruthenium complexes with NHC (N-heterocyclic carbene)-type bridging ligands have been prepared and structurally and photophysically characterised. The identity of the NHC-unit of the bridging ligand was established unambiguously by means of X-ray structural analysis of a heterodinuclear ruthenium–silver complex. The photophysical data indicate ultrafast intersystem crossing into an emissive and a non-emissive triplet excited state after excitation of the ruthenium centre. Exceptionally high luminescence quantum yields of up to 39% and long lifetimes of up to 2 μs are some of the triplet excited state characteristics. Preliminary studies into the visible light driven photocatalytic hydrogen formation show no induction phase and constant turnover frequencies that are independent on the concentration of the photocatalyst. In conclusion this supports the notion of a stable assembly under photocatalytic conditions

Interaction of hyperalgesia and sensory loss in complex regional pain syndrome type I (CRPS I)

Sensory abnormalities are a key feature of Complex Regional Pain Syndrome (CRPS). In order to characterise these changes in patients suffering from acute or chronic CRPS I, we used Quantitative Sensory Testing (QST) in comparison to an age and gender matched control group

Investigating Tissue Optical Properties and Texture Descriptors of the Retina in Patients with Multiple Sclerosis

PURPOSE: To assess the differences in texture descriptors and optical properties of retinal tissue layers in patients with multiple sclerosis (MS) and to evaluate their usefulness in the detection of neurodegenerative changes using optical coherence tomography (OCT) image segmentation. PATIENTS AND METHODS: 38 patients with MS were examined using Stratus OCT. The raw macular OCT data were exported and processed using OCTRIMA software. The enrolled eyes were divided into two groups, based on the presence of optic neuritis (ON) in the history (MSON+ group, n = 36 and MSON- group, n = 31). Data of 29 eyes of 24 healthy subjects (H) were used as controls. A total of seven intraretinal layers were segmented and thickness as well as optical parameters such as contrast, fractal dimension, layer index and total reflectance were measured. Mixed-model ANOVA analysis was used for statistical comparisons. RESULTS: Significant thinning of the retinal nerve fiber layer (RNFL), ganglion cell/inner plexiform layer complex (GCL+IPL) and ganglion cell complex (GCC, RNFL+GCL+IPL) was observed between study groups in all comparisons. Significant difference was found in contrast in the RNFL, GCL+IPL, GCC, inner nuclear layer (INL) and outer plexiform layer when comparing MSON+ to the other groups. Higher fractal dimension values were observed in GCL+IPL and INL layers when comparing H vs. MSON+ groups. A significant difference was found in layer index in the RNFL, GCL+IPL and GCC layers in all comparisons. A significant difference was observed in total reflectance in the RNFL, GCL+IPL and GCC layers between the three examination groups. CONCLUSION: Texture and optical properties of the retinal tissue undergo pronounced changes in MS even without optic neuritis. Our results may help to further improve the diagnostic efficacy of OCT in MS and neurodegeneration

The GRAVITY young stellar object survey XIII. Tracing the time-variable asymmetric disk structure in the inner AU of the Herbig star HD98922

Temporal variability in the photometric and spectroscopic properties of protoplanetary disks is common in YSO. However, evidence pointing toward changes in their morphology over short timescales has only been found for a few sources, mainly due to a lack of high cadence observations at mas resolution. We combine GRAVITY multi-epoch observations of HD98922 at mas resolution with PIONIER archival data covering a total time span of 11 years. We interpret the interferometric visibilities and spectral energy distribution with geometrical models and through radiative transfer techniques. We investigated high-spectral-resolution quantities to obtain information on the properties of the HI BrG-line-emitting region. The observations are best fitted by a model of a crescent-like asymmetric dust feature located at 1 au and accounting for 70% of the NIR emission. The feature has an almost constant magnitude and orbits the central star with a possible sub-Keplerian period of 12 months, although a 9 month period is another, albeit less probable, solution. The radiative transfer models show that the emission originates from a small amount of carbon-rich (25%) silicates, or quantum-heated particles located in a low-density region. Among different possible scenarios, we favor hydrodynamical instabilities in the inner disk that can create a large vortex. The high spectral resolution differential phases in the BrG-line show that the hot-gas component is offset from the star and in some cases is located between the star and the crescent feature. The scale of the emission does not favor magnetospheric accretion as a driving mechanism. The scenario of an asymmetric disk wind or a massive accreting substellar or planetary companion is discussed. With this unique observational data set for HD98922, we reveal morphological variability in the innermost 2 au of its disk region.Comment: 45 pages, 20 figures, accepted by and to be published in Astronomy & Astrophysics (A&A