Star-shaped oligofluorene truxene macromolecules – synthesis and properties as a function of alkyl chain length (PH-11611YP)

Star-shaped oligofluorene truxenes are very promising materials and have demonstrated excellent properties as the gain medium in organic semiconductor lasers (OSLs).1-10 Alkyl chains in oligofluorene truxenes act as solubilizing groups as well as spacers to prevent intermolecular π-π stacking that leads to quenching of the light emission. A new series of star-shaped systems analogous to hexyl oligofluorene truxenes11 with alkyl chains of different lengths (butyl chains and octyl chains) was synthesized. The objective of this study was to investigate the effect of alkyl chain length on the film-forming properties of oligofluorene-truxene materials and, as a result, on their optoelectronic properties for applications as the gain medium in OSLs

A saturated red color converter for visible light communication using a blend of star-shaped organic semiconductors

Authors would like to acknowledge the EPSRC for financial support for the UP-VLC (EP/K00042X/1). PJS and IDWS also acknowledge Royal Society Wolfson Research Merit Awards.We report a study of blends of semiconducting polymers as saturated red color converters to replace commercial phosphors in hybrid LEDs for visible light communication (VLC). By blending two star-shaped organic semiconductor molecules, we found a near complete energy transfer (> 90% efficiency) from the green-emitting truxene-cored compound T4BT-B to the red-emitting boron dipyrromethene (BODIPY) cored materials. Furthermore, we have demonstrated the capability of these materials as fast color converters for VLC by measuring their intrinsic optical modulation bandwidth and data rate. The measured 3 dB modulation bandwidth of blends (~55 MHz) is more than 10 times higher than commercially available LED phosphors and also higher than the red-emitting BODIPY color converter alone in solution. The data rate achieved with this blend is 20 times higher than measured with a commercially available phosphor based color converter.PostprintPeer reviewe

Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1–T-B4 and Y-B1–Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications

Synthesis and properties of novel star-shaped oligofluorene conjugated systems with BODIPY cores

Star-shaped conjugated systems with varying oligofluorene arm length and substitution patterns of the central BODIPY core have been synthesised, leading to two families of compounds, T-B1-T-B4 and Y-B1-Y-B4, with T- and Y-shaped motifs, respectively. Thermal stability, cyclic voltammetry, absorption and photoluminescence spectroscopy of each member of these two families were studied in order to determine their suitability as emissive materials in photonic applications

Side-chain influence on the mass density and refractive index of polyfluorenes and star-shaped oligofluorene truxenes

The density of organic semiconductor films is an important quantity because it is related to intermolecular spacing which in turn determines the electronic and photophysical properties. We report thin film density and refractive index measurements of polyfluorenes and star-shaped oligofluorene truxene molecules. An ellipsometer and a procedure using a spectrophotometer were used to determine film thickness and mass of spin-coated films, respectively. We present a study of the effect of alkyl side-chain length on the volumetric mass density and refractive index of the materials studied. The density measured for poly(9,9-di-n-octylfluorene) (PF8) was 0.88 ± 0.04 g/cm3 and decreased with longer alkyl side chains. For the truxene molecule with butyl side chains (T3 butyl), we measured a density of 0.90 ± 0.04 g/cm3, which also decreased with increasing side-chain length

Developing and paying for medicines for orphan indications in oncology: utilitarian regulation vs equitable care?

Despite ‘orphan drug' legislation, bringing new medicines for rare diseases to market and securing funding for their provision is sometimes both costly and problematic, even in the case of medicines for very rare ‘ultra orphan' oncological indications. In this paper difficulties surrounding the introduction of a new treatment for osteosarcoma exemplify the challenges that innovators can face. The implications of current policy debate on ‘value-based' medicines pricing in Europe, North America and elsewhere are also explored in the context of sustaining research into and facilitating cancer patient access to medicines for low-prevalence indications. Tensions exist between utilitarian strategies aimed at optimising the welfare of the majority in the society and minority-interest-focused approaches to equitable care provision. Current regulatory and pricing strategies should be revisited with the objective of facilitating fair and timely drug supply to patients without sacrificing safety or overall affordability. Failures effectively to tackle the problems considered here could undermine public interests in developing better therapies for cancer patients

Impact of social determinants on antiretroviral therapy access and outcomes entering the era of universal treatment for people living with HIV in Italy

Background: Social determinants are known to be a driving force of health inequalities, even in high income countries. Aim of our study was to determine if these factors can limit antiretroviral therapy (ART) access, outcome and retention in care of people living with HIV (PLHIV) in Italy. Methods: All ART naïve HIV+ patients (pts) of Italian nationality enrolled in the ICONA Cohort from 2002 to 2016 were included. The association of socio-demographic characteristics (age, sex, risk factor for HIV infection, educational level, occupational status and residency area) with time to: ART initiation (from the first positive anti-HIV test), ART regimen discontinuation, and first HIV-RNA < 50 cp/mL, were evaluated by Cox regression analysis, Kaplan Meier method and log-rank test. Results: A total of 8023 HIV+ pts (82% males, median age at first pos anti-HIV test 36 years, IQR: 29-44) were included: 6214 (77.5%) started ART during the study period. Women, people who inject drugs (PWID) and residents in Southern Italy presented the lowest levels of education and the highest rate of unemployment compared to other groups. Females, pts aged > 50 yrs., unemployed vs employed, and people with lower educational levels presented the lowest CD4 count at ART initiation compared to other groups. The overall median time to ART initiation was 0.6 years (yrs) (IQR 0.1-3.7), with a significant decrease over time [2002-2006 = 3.3 yrs. (0.2-9.4); 2007-2011 = 1.0 yrs. (0.1-3.9); 2012-2016 = 0.2 yrs. (0.1-2.1), p < 0.001]. By multivariate analysis, females (p < 0.01) and PWID (p < 0.001), presented a longer time to ART initiation, while older people (p < 0.001), people with higher educational levels (p < 0.001), unemployed (p = 0.02) and students (p < 0.001) were more likely to initiate ART. Moreover, PWID, unemployed vs stable employed, and pts. with lower educational levels showed a lower 1-year probability of achieving HIV-RNA suppression, while females, older patients, men who have sex with men (MSM), unemployed had higher 1-year risk of first-line ART discontinuation. Conclusions: Despite median time to ART start decreased from 2002 to 2016, socio-demographic factors still contribute to disparities in ART initiation, outcome and durability

The mineral composition and spatial distribution of the dust ejecta of NGC 6302

We have analysed the full ISO spectrum of the planetary nebula NGC 6302 in order to derive the mineralogical composition of the dust in the nebula. We use an optically thin dust model in combination with laboratory measurements of cosmic dust analogues. We find two main temperature components at about 100 and 50 K respectively, with distinctly different dust compositions. The warm component contains an important contribution from dust without strong infrared resonances. In particular the presence of small warm amorphous silicate grains can be excluded. The detection of weak PAH bands also points to a peculiar chemical composition of the dust in this oxygen-rich nebula. The cool dust component contains the bulk of the mass and shows strong emission from crystalline silicates, which contain about 10 percent of the mass. In addition, we identify the 92 micron band with the mineral calcite, and argue that the 60 micron band contains a contribution from the carbonate dolomite. We present the mass absorption coefficients of six different carbonate minerals. The geometry of the dust shell around NGC 6302 is studied with mid-infrared images obtained with TIMMI2. We argue that the cool dust component is present in a circumstellar dust torus, while the diffuse emission from the warm component originates from the lobes.Comment: 13 pages, 10 figures, accepted for publication in A&

Morphological effects on IR band profiles: Experimental spectroscopic analysis with application to observed spectra of oxygen-rich AGB stars

To trace the source of the unique 13, 19.5, and 28 $\mu$m emission features in the spectra of oxygen-rich circumstellar shells around AGB stars, we have compared dust extinction spectra obtained by aerosol measurements. We have measured the extinction spectra for 19 oxide powder samples of eight different types, such as Ti-compounds (TiO, TiO$_2$, Ti$_2$O$_3$, Ti$_3$O$_5$, Al$_2$TiO$_5$, CaTiO$_3$), $\alpha$-, $\gamma$-, $\chi$-$\delta$-$\kappa$-Al$_2$O$_3$, and MgAl$_2$O$_4$ in the infrared region (10 - 50 $\mu$m) paying special attention to the morphological (size, shape, and agglomeration) effects and the differences in crystal structure. Anatase (TiO$_2$) particles with rounded edges are the possible 13, 19.5 and 28 $\mu$m band carriers as the main contributor in the spectra of AGB stars, and spherically shaped nano-sized spinel and Al$_2$TiO$_5$ dust grains are possibly associated with the anatase, enhancing the prominence of the 13 $\mu$m feature and providing additional features at 28 $\mu$m. The extinction data sets obtained by the aerosol and CsI pellet measurements have been made available for public use at http://elbe.astro.uni-jena.deComment: 17 pages, 8 figures, Accepted 24 March 2009 for publication in A&

The Planetary Fourier Spectrometer (PFS) onboard the European Mars Express mission

International audience; The Planetary Fourier Spectrometer (PFS) for the Mars Express mission is an infrared spectrometer optimised for atmospheric studies. This instrument has a short wave (SW) channel that covers the spectral range from 1700 to 8200.0cm-1 (1.2- 5.5mum) and a long-wave (LW) channel that covers 250- 1700cm-1 (5.5- 45mum). Both channels have a uniform spectral resolution of 1.3cm-1. The instrument field of view FOV is about 1.6o (FWHM) for the Short Wavelength channel (SW) and 2.8o (FWHM) for the Long Wavelength channel (LW) which corresponds to a spatial resolution of 7 and 12 km when Mars is observed from an height of 250 km. PFS can provide unique data necessary to improve our knowledge not only of the atmosphere properties but also about mineralogical composition of the surface and the surface-atmosphere interaction. The SW channel uses a PbSe detector cooled to 200-220 K while the LW channel is based on a pyroelectric ( LiTaO3) detector working at room temperature. The intensity of the interferogram is measured every 150 nm of physical mirrors displacement, corresponding to 600 nm optical path difference, by using a laser diode monochromatic light interferogram (a sine wave), whose zero crossings control the double pendulum motion. PFS works primarily around the pericentre of the orbit, only occasionally observing Mars from large distances. Each measurements take 4 s, with a repetition time of 8.5 s. By working roughly 0.6 h around pericentre, a total of 330 measurements per orbit will be acquired 270 looking at Mars and 60 for calibrations. PFS is able to take measurements at all local times, facilitating the retrieval of surface temperatures and atmospheric vertical temperature profiles on both the day and the night side