Ultrafast Structure and Dynamics in the Thermally Activated Delayed Fluorescence of a Carbene-Metal-Amide

Thermally activated delayed fluorescence has enormous potential for the development of efficient light emitting diodes. A recently discovered class of molecules (the carbene – metal – amides, CMAs) are exceptionally promising as they combine the small singlet - triplet energy gap required for thermal activation with a large transition moment for emission. Calculations suggest that excited state structural dynamics modulate the critical coupling between singlet and triplet states, but do not agree on the nature of those dynamics. Here we report ultrafast time resolved transient absorption and Raman studies of CMA photodynamics. The measurements reveal complex structural evolution following intersystem crossing on the tens to hundreds of picoseconds timescale, and a change in the low frequency vibrational spectrum between singlet and triplet states. The latter is assigned to a change in frequency or amplitude associated with a Raman active mode localized on the metal centre

Plausible home stars of the interstellar object 'Oumuamua found in Gaia DR2

The first detected interstellar object 'Oumuamua that passed within 0.25au of the Sun on 2017 September 9 was presumably ejected from a stellar system. We use its newly determined non-Keplerian trajectory together with the reconstructed Galactic orbits of 7 million stars from Gaia DR2 to identify past close encounters. Such an "encounter" could reveal the home system from which 'Oumuamua was ejected. The closest encounter, at 0.60pc (0.53-0.67pc, 90% confidence interval), was with the M2.5 dwarf HIP 3757 at a relative velocity of 24.7km/s, 1Myr ago. A more distant encounter (1.6pc) but with a lower encounter (ejection) velocity of 10.7km/s was with the G5 dwarf HD 292249, 3.8Myr ago. Two more stars have encounter distances and velocities intermediate to these. The encounter parameters are similar across six different non-gravitational trajectories for 'Oumuamua. Ejection of 'Oumuamua by scattering from a giant planet in one of the systems is plausible, but requires a rather unlikely configuration to achieve the high velocities found. A binary star system is more likely to produce the observed velocities. None of the four home candidates have published exoplanets or are known to be binaries. Given that the 7 million stars in Gaia DR2 with 6D phase space information is just a small fraction of all stars for which we can eventually reconstruct orbits, it is a priori unlikely that our current search would find 'Oumuamua's home star system. As 'Oumuamua is expected to pass within 1pc of about 20 stars and brown dwarfs every Myr, the plausibility of a home system depends also on an appropriate (low) encounter velocity.Comment: Accepted to The Astronomical Journa

Thermal evolution and activity of Comet 9P/Tempel 1 and simulation of a deep impact

We use a quasi 3-D thermal evolution model for a spherical comet nucleus, which takes into account the diurnal and latitudinal variation of the solar flux, but neglects lateral heat conduction. We model the thermal evolution and activity of Comet 9P/Tempel 1, in anticipation of the Deep Impact mission encounter with the comet. We also investigate the possible outcome of a projectile impact, assuming that all the energy is absorbed as thermal energy. An interesting result of this investigation, is that the estimated amount of dust ejected due to the impact is equivalent to 2--2.6 days of activity, during "quiet" conditions, at perihelion. We show that production rates of volatiles that are released in the interior of the nucleus depend strongly on the porous structure, in particular on the surface to volume ratio of the pores. We develop a more accurate model for calculating this parameter, based on a distribution of pore sizes, rather than a single, average pore size.Comment: 25 pages, 8 figures, accepted for publication in PASP (in press). For fig.xx (composite image, sec.4) and a better resolution of fig.6 see, http://geophysics.tau.ac.il/personal/gal%5Fsarid

Temporal and Spatial Aspects of Gas Release During the 2010 Apparition of Comet 103P/Hartley-2

We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet 103P/Hartley-2 using high dispersion infrared spectroscopy. We quantified the long- and short-term behavior of volatile release over a three-month interval that encompassed the comet's close approach to Earth, its perihelion passage, and flyby of the comet by the Deep Impact spacecraft during the EPOXI mission. We present production rates for individual species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates. The production rates for water, ethane, HCN, and methanol vary in a manner consistent with independent measures of nucleus rotation, but mixing ratios for HCN, C2H6, & CH3OH are independent of rotational phase. Our results demonstrate that the ensemble average composition of gas released from the nucleus is well defined, and relatively constant over the three-month interval (September 18 through December 17). If individual vents vary in composition, enough diverse vents must be active simultaneously to approximate (in sum) the bulk composition of the nucleus. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps (and also, directly from the nucleus), and provide insights into the driver for the cyanogen (CN) polar jet. The spatial distributions of C2H6 & HCN along the near-polar jet (UT 19.5 October) and nearly orthogonal to it (UT 22.5 October) are discussed relative to the origin of CN. The ortho-para ratio (OPR) of water was 2.85 \pm 0.20; the lower bound (2.65) defines Tspin > 32 K. These values are consistent with results returned from ISO in 1997.Comment: 18 pages, 3 figures, to be published in: Astrophysical Journal Letter

Sub-wavelength surface IR imaging of soft-condensed matter

Outlined here is a technique for sub-wavelength infrared surface imaging performed using a phase matched optical parametric oscillator laser and an atomic force microscope as the detection mechanism. The technique uses a novel surface excitation illumination approach to perform simultaneously chemical mapping and AFM topography imaging with an image resolution of 200 nm. This method was demonstrated by imaging polystyrene micro-structures

Potential link between the Sphingosine-1-Phosphate (S1P) system and defective alveolar macrophage phagocytic function in Chronic Obstructive Pulmonary Disease (COPD)

We previously reported that alveolar macrophages from patients with chronic obstructive pulmonary disease (COPD) are defective in their ability to phagocytose apoptotic cells, with a similar defect in response to cigarette smoke. The exact mechanisms for this defect are unknown. Sphingolipids including ceramide, sphingosine and sphingosine-1-phosphate (S1P) are involved in diverse cellular processes and we hypothesised that a comprehensive analysis of this system in alveolar macrophages in COPD may help to delineate the reasons for defective phagocytic function.We compared mRNA expression of sphingosine kinases (SPHK1/2), S1P receptors (S1PR1-5) and S1P-degrading enzymes (SGPP1, SGPP2, SGPL1) in bronchoalveolar lavage-derived alveolar macrophages from 10 healthy controls, 7 healthy smokers and 20 COPD patients (10 current- and 10 ex-smokers) using Real-Time PCR. Phagocytosis of apoptotic cells was investigated using flow cytometry. Functional associations were assessed between sphingosine signalling system components and alveolar macrophage phagocytic ability in COPD. To elucidate functional effects of increased S1PR5 on macrophage phagocytic ability, we performed the phagocytosis assay in the presence of varying concentrations of suramin, an antagonist of S1PR3 and S1PR5. The effects of cigarette smoking on the S1P system were investigated using a THP-1 macrophage cell line model.We found significant increases in SPHK1/2 (3.4- and 2.1-fold increases respectively), S1PR2 and 5 (4.3- and 14.6-fold increases respectively), and SGPL1 (4.5-fold increase) in COPD vs. controls. S1PR5 and SGPL1 expression was unaffected by smoking status, suggesting a COPD "disease effect" rather than smoke effect per se. Significant associations were noted between S1PR5 and both lung function and phagocytosis. Cigarette smoke extract significantly increased mRNA expression of SPHK1, SPHK2, S1PR2 and S1PR5 by THP-1 macrophages, confirming the results in patient-derived macrophages. Antagonising SIPR5 significantly improved phagocytosis.Our results suggest a potential link between the S1P signalling system and defective macrophage phagocytic function in COPD and advise therapeutic targets.Jameel Barnawi, Hai Tran, Hubertus Jersmann, Stuart Pitson, Eugene Roscioli, Greg Hodge, Robyn Meech, Rainer Haberberger, Sandra Hodg