Modelling of the 10-micrometer natural laser emission from the mesospheres of Mars and Venus

The NLTE radiative transfer problem is solved to obtain the 00 deg 1 vibrational state population. This model successfully reproduces the existing center-to-limb observations, although higher spatial resolution observations are needed for a definitive test. The model also predicts total fluxes which are close to the observed values. The strength of the emission is predicted to be closely related to the instantaneous near-IR solar heating rate

Self-Sorting Microscale Compartmentalized Block Copolypeptide Hydrogels

Multicomponent interpenetrating network hydrogels possessing enhanced mechanical stiffness compared to their individual components were prepared via physical mixing of diblock copolypeptides that assemble by either hydrophobic association or polyion complexation in aqueous media. Optical microscopy analysis of fluorescent-probe-labeled multicomponent hydrogels revealed that the diblock copolypeptide components rapidly and spontaneously self-sort to form distinct hydrogel networks that interpenetrate at micron length scales. These materials represent a class of microscale compartmentalized hydrogels composed of degradable, cell-compatible components, which possess rapid self-healing properties and independently tunable domains for downstream applications in biology and additive manufacturing

Influence of Sulfoxide Group Placement on Polypeptide Conformational Stability.

The synthesis of a homologous series containing five new nonionic sulfoxide containing polypeptides was described. Sulfoxide groups bestowed water solubility for all homologues, which allowed their use as a model for study of helix-coil transitions in water while avoiding contributions from charged groups or phase separation. Polypeptides were found to adopt chain conformations in water that were dependent on distance of sulfoxides from chain backbones, overall side-chain lengths, and solvent. These results allow preparation of polypeptide segments with different chain conformations without changing chemical functionality for potential use in structural studies and functional applications

Self-Healing Multiblock Copolypeptide Hydrogels via Polyion Complexation

Diblock, triblock, and pentablock copolypeptides were designed and prepared for formation of polyion complex hydrogels in aqueous media. Increasing the number of block segments was found to allow formation of hydrogels with substantially enhanced stiffness at equivalent concentrations. Use of similar length ionic segments also allowed mixing of different block architectures to fine-tune hydrogel properties. The pentablock hydrogels possess a promising combination of high stiffness, rapid self-healing properties, and cell compatible surface chemistry that makes them promising candidates for applications requiring injectable or printable hydrogel scaffolds

Tunable, Functional Diblock Copolypeptide Hydrogels Based on Methionine Homologs.

The preparation of new diblock copolypeptide hydrogels derived from homologs of l-methionine, that is, l-homomethionine and l-6-(methylthio)-l-norleucine is described. Compared to l-methionine residues, use of l-methionine homologs allow improved copolymerization with l-leucine residues to give well-defined block copolypeptides. These copolypeptides are subsequently modified using robust thioether alkylation reactions employing a variety of functional epoxides, which yield samples capable of forming transparent, self-healing hydrogels in water. The facile variation of different functional epoxides for postpolymerization modification is found to allow predictable functionalization and tuning of hydrogel properties by the modification of simple precursors

Spitzer Secondary Eclipses of Qatar-1b

Previous secondary eclipse observations of the hot Jupiter Qatar-1b in the Ks band suggest that it may have an unusually high day side temperature, indicative of minimal heat redistribution. There have also been indications that the orbit may be slightly eccentric, possibly forced by another planet in the system. We investigate the day side temperature and orbital eccentricity using secondary eclipse observations with Spitzer. We observed the secondary eclipse with Spitzer/IRAC in subarray mode, in both 3.6 and 4.5 micron wavelengths. We used pixel-level decorrelation to correct for Spitzer's intra-pixel sensitivity variations and thereby obtain accurate eclipse depths and central phases. Our 3.6 micron eclipse depth is 0.149 +/- 0.051% and the 4.5 micron depth is 0.273 +/- 0.049%. Fitting a blackbody planet to our data and two recent Ks band eclipse depths indicates a brightness temperature of 1506 +/- 71K. Comparison to model atmospheres for the planet indicates that its degree of longitudinal heat redistribution is intermediate between fully uniform and day side only. The day side temperature of the planet is unlikely to be as high (1885K) as indicated by the ground-based eclipses in the Ks band, unless the planet's emergent spectrum deviates strongly from model atmosphere predictions. The average central phase for our Spitzer eclipses is 0.4984 +/- 0.0017, yielding e cos(omega) = -0.0028 +/- 0.0027. Our results are consistent with a circular orbit, and we constrain e cos(omega) much more strongly than has been possible with previous observations

Updated Spitzer Emission Spectroscopy of Bright Transiting Hot Jupiter HD189733b

We analyze all existing secondary eclipse time series spectroscopy of hot Jupiter HD189733b acquired with the now defunct Spitzer/IRS instrument. We describe the novel approaches we develop to remove the systematic effects and extract accurate secondary eclipse depths as a function of wavelength in order to construct the emission spectrum of the exoplanet. We compare our results to a previous study by Grillmair et al. that did not examine all data sets available to us. We are able to confirm the detection of a water feature near 6{\mu}m claimed by Grillmair et al. We compare the planetary emission spectrum to three model families -- based on isothermal atmosphere, gray atmosphere, and two realizations of the complex radiative transfer model by Burrows et al., adopted in Grillmair et al.'s study. While we are able to reject the simple isothermal and gray models based on the data at the 97% level just from the IRS data, these rejections hinge on eclipses measured within relatively narrow wavelength range, between 5.5 and 7{\mu}m. This underscores the need for observational studies with broad wavelength coverage and high spectral resolution, in order to obtain robust information on exoplanet atmospheres.Comment: 16 pages, 13 figures and 3 tables. Accepted for publication in Ap

Influence of Sulfur-Containing Diamino Acid Structure on Covalently Crosslinked Copolypeptide Hydrogels.

Biologically occurring non-canonical di-α-amino acids were converted into new di-N-carboxyanhydride (di-NCA) monomers in reasonable yields with high purity. Five different di-NCAs were separately copolymerized with tert-butyl-l-glutamate NCA to obtain covalently crosslinked copolypeptides capable of forming hydrogels with varying crosslinker density. Comparison of hydrogel properties with residue structure revealed that different di-α-amino acids were not equivalent in crosslink formation. Notably, l-cystine was found to produce significantly weaker hydrogels compared to l-homocystine, l-cystathionine, and l-lanthionine, suggesting that l-cystine may be a sub-optimal choice of di-α-amino acid for preparation of copolypeptide networks. The di-α-amino acid crosslinkers also provided different chemical stability, where disulfide crosslinks were readily degraded by reduction, and thioether crosslinks were stable against reduction. This difference in response may provide a means to fine tune the reduction sensitivity of polypeptide biomaterial networks

Homoallylglycine residues are superior precursors to orthogonally modified thioether containing polypeptides.

Homoallylglycine N-carboxyanhydride, Hag NCA, monomers were synthesized and used to prepare polypeptides containing Hag segments with controllable lengths of up to 245 repeats. Poly(l-homoallylglycine), GHA, was found to adopt an α-helical conformation, which provided good solubility in organic solvents and allowed high yield functionalization of its alkene side-chains via radical promoted addition of thiols. The conformations of these derivatives were shown to be switchable between α-helical and disordered states in aqueous media using thioether alkylation or oxidation reactions. Incorporation of GHA segments into block copolymers with poly(l-methionine), M, segments provided a means to orthogonally modify thioether side-chains different ways in separate copolypeptide domains. This approach allows preparation of functional polypeptides containing discrete domains of oxidized and alkylated thioether containing residues, where chain conformation and functionality of each domain can be independently modified