Time resolved structural dynamics of butadiyne-linked porphyrin dimers

In this work the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump / broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through addition of a ligand, provide conclusive evidence for the twisting motion performed by the porphyrin dimer in solution

An alternate proton acceptor for excited-state proton transfer in green fluorescent protein: Rewiring GFP

The neutral form of the chromophore in wild-type green fluorescent protein (wtGFP) undergoes excited-state proton transfer (ESPT) upon excitation, resulting in characteristic green (508 nm) fluorescence. This ESPT reaction involves a proton relay from the phenol hydroxyl of the chromophore to the ionized side chain of E222, and results in formation of the anionic chromophore in a protein environment optimized for the neutral species (the I* state). Reorientation or replacement of E222, as occurs in the S65T and E222Q GFP mutants, disables the ESPT reaction and results in loss of green emission following excitation of the neutral chromophore. Previously, it has been shown that the introduction of a second mutation (H148D) into S65T GFP allows the recovery of green emission, implying that ESPT is again possible. A similar recovery of green fluorescence is also observed for the E222Q/H148D mutant, suggesting that D148 is the proton acceptor for the ESPT reaction in both double mutants. The mechanism of fluorescence emission following excitation of the neutral chromophore in S65T/H148D and E222Q/H148D has been explored through the use of steady state and ultrafast time-resolved fluorescence and vibrational spectroscopy. The data are contrasted with those of the single mutant S65T GFP. Time-resolved fluorescence studies indicate very rapid (<1 ps) formation of I* in the double mutants, followed by vibrational cooling on the picosecond time scale. The time-resolved IR difference spectra are markedly different to those of wtGFP or its anionic mutants. In particular, no spectral signatures are apparent in the picosecond IR difference spectra that would correspond to alteration in the ionization state of D148, leading to the proposal that a low-barrier hydrogen bond (LBHB) is present between the phenol hydroxyl of the chromophore and the side chain of D148, with different potential energy surfaces for the ground and excited states. This model is consistent with recent high-resolution structural data in which the distance between the donor and acceptor oxygen atoms is =2.4 Å. Importantly, these studies indicate that the hydrogen-bond network in wtGFP can be replaced by a single residue, an observation which, when fully explored, will add to our understanding of the various requirements for proton-transfer reactions within proteins

Hubble Space Telescope Observations of Comet 9P/Tempel 1 during the Deep Impact Encounter

We report on the Hubble Space Telescope program to observe periodic comet 9P/Tempel 1 in conjunction with NASA's Deep Impact mission. Our objectives were to study the generation and evolution of the coma resulting from the impact and to obtain wide-band images of the visual outburst generated by the impact. Two observing campaigns utilizing a total of 17 HST orbits were carried out: the first occurred on 2005 June 13-14 and fortuitously recorded the appearance of a new, short-lived fan in the sunward direction on June 14. The principal campaign began two days before impact and was followed by contiguous orbits through impact plus several hours and then snapshots one, seven, and twelve days later. All of the observations were made using the Advanced Camera for Surveys (ACS). For imaging, the ACS High Resolution Channel (HRC) provides a spatial resolution of 36 km (16 km/pixel) at the comet at the time of impact. Baseline images of the comet, made prior to impact, photometrically resolved the comet's nucleus. The derived diameter, 6.1 km, is in excellent agreement with the 6.0 +/- 0.2 km diameter derived from the spacecraft imagers. Following the impact, the HRC images illustrate the temporal and spatial evolution of the ejecta cloud and allow for a determination of its expansion velocity distribution. One day after impact the ejecta cloud had passed out of the field-of-view of the HRC.Comment: 15 pages, 14 postscript figures. Accepted for publication in Icarus special issue on Deep Impac

Vibronic interactions in the visible and near-infrared spectra of C60− anions

Electron-phonon coupling is an important factor in understanding many properties of the C60 fullerides. However, there has been little success in quantifying the strength of the vibronic coupling in C60 ions, with considerable disagreement between experimental and theoretical results. We will show that neglect of quadratic coupling in previous models for C60- ions results in a significant overestimate of the linear coupling constants. Including quadratic coupling allows a coherent interpretation to be made of earlier experimental and theoretical results which at first sight are incompatible

The formation heritage of Jupiter Family Comet 10P/Tempel 2 as revealed by infrared spectroscopy

We present spectral and spatial information for major volatile species in Comet 10P/Tempel 2, based on high-dispersion infrared spectra acquired on UT 2010 July 26 (heliocentric distance Rh = 1.44 AU) and September 18 (Rh = 1.62 AU), following the comet's perihelion passage on UT 2010 July 04. The total production rate for water on July 26 was (1.90 +/- 0.12) x 10^28 molecules s-1, and abundances of six trace gases (relative to water) were: CH3OH (1.58% +/- 0.23), C2H6 (0.39% +/- 0.04), NH3 (0.83% +/- 0.20), and HCN (0.13% +/- 0.02). A detailed analysis of intensities for water emission lines provided a rotational temperature of 35 +/- 3 K. The mean OPR is consistent with nuclear spin populations in statistical equilibrium (OPR = 3.01 +/- 0.18), and the (1-sigma) lower bound corresponds to a spin temperature > 38 K. Our measurements were contemporaneous with a jet-like feature observed at optical wavelengths. The spatial profiles of four primary volatiles display strong enhancements in the jet direction, which favors release from a localized vent on the nucleus. The measured IR continuum is much more sharply peaked and is consistent with a dominant contribution from the nucleus itself. The peak intensities for H2O, CH3OH, and C2H6 are offset by ~200 km in the jet direction, suggesting the possible existence of a distributed source, such as the release of icy grains that subsequently sublimed in the coma. On UT September 18, no obvious emission lines were present in our spectra, nevertheless we obtained a 3-sigma upper limit Q(H2O) < 2.86 x 10^27 molecules s-1

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

WISE/NEOWISE Preliminary Analysis and Highlights of the 67P/Churyumov-Gerasimenko Near Nucleus Environs

On January 18-19 and June 28-29 of 2010, the Wide-field Infrared Survey Explorer (WISE) spacecraft imaged the Rosetta mission target, comet 67P/Churyumov-Gerasimenko. We present a preliminary analysis of the images, which provide a characterization of the dust environment at heliocentric distances similar to those planned for the initial spacecraft encounter, but on the outbound leg of its orbit rather than the inbound. Broad-band photometry yields low levels of CO2 production at a comet heliocentric distance of 3.32 AU and no detectable production at 4.18 AU. We find that at these heliocentric distances, large dust grains with mean grain diameters on the order of a millimeter or greater dominate the coma and evolve to populate the tail. This is further supported by broad-band photometry centered on the nucleus, which yield an estimated differential dust particle size distribution with a power law relation that is considerably shallower than average. We set a 3-sigma upper limit constraint on the albedo of the large-grain dust at <= 0.12. Our best estimate of the nucleus radius (1.82 +/- 0.20 km) and albedo (0.04 +/- 0.01) are in agreement with measurements previously reported in the literature

Cometary activity in 2060 Chiron at minimum brightness

We present two-colour CCD imaging of 2060 Chiron obtained between 1996 and 1998 with the 2.15 m telescope at CASLEO (San Juan, Argentina). These post-perihelion observations show that Chiron was then near its historical brightness minima, however a coma was clearly detected. The dynamical state of the coma is studied by means of azimuthally averaged surface brightness profiles, which show the signatures of radiation pressure on the dust grain distribution. Aperture photometry shows an achromatic dimming with an amplitude \~ 0.09 mag in approximately one hour. If due to rotation of the nucleus, this rather high amplitude is used to derive a new value for the nuclear magnitude, m_0 ~ 6.80 mag.Comment: Accepted for publication in Planetary and Space Scienc

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