Infrared spectroscopy of HCOOH in interstellar ice analogues

Context: HCOOH is one of the more common species in interstellar ices with abundances of 1-5% with respect to solid H2O. Aims: This study aims at characterizing the HCOOH spectral features in astrophysically relevant ice mixtures in order to interpret astronomical data. Methods: The ices are grown under high vacuum conditions and spectra are recorded in transmission using a Fourier transform infrared spectrometer. Pure HCOOH ices deposited at 15 K and 145 K are studied, as well as binary and tertiary mixtures containing H2O, CO, CO2 and CH3OH. The mixture concentrations are varied from 50:50% to ~10:90% for HCOOH:H2O. Binary mixtures of HCOOH:X and tertiary mixtures of HCOOH:H2O:X with X = CO, CO2, and CH3OH, are studied for concentrations of ~10:90% and ~7:67:26%, respectively. Results: Pure HCOOH ice spectra show broad bands which split around 120 K due to the conversion of a dimer to a chain-structure. Broad single component bands are found for mixtures with H2O. Additional spectral components are present in mixtures with CO, CO2 and CH3OH. The resulting peak position, full width at half maximum and band strength depend strongly on ice structure, temperature, matrix constituents and the HCOOH concentration. Comparison of the solid HCOOH 5.9, 7.2, and 8.1 micron features with astronomical data toward the low mass source HH 46 and high mass source W 33A shows that spectra of binary mixtures do not reproduce the observed ice features. However, our tertiary mixtures especially with CH3OH match the astronomical data very well. Thus interstellar HCOOH is most likely present in tertiary or more complex mixtures with H2O, CH3OH and potentially also CO or CO2, providing constraints on its formation.Comment: 11 pages, 10 figures, accepted by A&

Collision Dynamics and Solvation of Water Molecules in a Liquid Methanol Film

Environmental molecular beam experiments are used to examine water interactions with liquid methanol films at temperatures from 170 K to 190 K. We find that water molecules with 0.32 eV incident kinetic energy are efficiently trapped by the liquid methanol. The scattering process is characterized by an efficient loss of energy to surface modes with a minor component of the incident beam that is inelastically scattered. Thermal desorption of water molecules has a well characterized Arrhenius form with an activation energy of 0.47{\pm}0.11 eV and pre-exponential factor of 4.6 {\times} 10^(15{\pm}3) s^(-1). We also observe a temperature dependent incorporation of incident water into the methanol layer. The implication for fundamental studies and environmental applications is that even an alcohol as simple as methanol can exhibit complex and temperature dependent surfactant behavior.Comment: 8 pages, 5 figure

Characterization of the Endothelial Cell Cytoskeleton following HLA Class I Ligation

Vascular endothelial cells (ECs) are a target of antibody-mediated allograft rejection. In vitro, when the HLA class I molecules on the surface of ECs are ligated by anti-HLA class I antibodies, cell proliferation and survival pathways are activated and this is thought to contribute to the development of antibody-mediated rejection. Crosslinking of HLA class I molecules by anti-HLA antibodies also triggers reorganization of the cytoskeleton, which induces the formation of F-actin stress fibers. HLA class I induced stress fiber formation is not well understood.The present study examines the protein composition of the cytoskeleton fraction of ECs treated with HLA class I antibodies and compares it to other agonists known to induce alterations of the cytoskeleton in endothelial cells. Analysis by tandem mass spectrometry revealed unique cytoskeleton proteomes for each treatment group. Using annotation tools a candidate list was created that revealed 12 proteins, which were unique to the HLA class I stimulated group. Eleven of the candidate proteins were phosphoproteins and exploration of their predicted kinases provided clues as to how these proteins may contribute to the understanding of HLA class I induced antibody-mediated rejection. Three of the candidates, eukaryotic initiation factor 4A1 (eIF4A1), Tropomyosin alpha 4-chain (TPM4) and DDX3X, were further characterized by Western blot and found to be associated with the cytoskeleton. Confocal microscopy analysis showed that class I ligation stimulated increased eIF4A1 co-localization with F-actin and paxillin.Colocalization of eIF4A1 with F-actin and paxillin following HLA class I ligation suggests that this candidate protein could be a target for understanding the mechanism(s) of class I mediated antibody-mediated rejection. This proteomic approach for analyzing the cytoskeleton of ECs can be applied to other agonists and various cells types as a method for uncovering novel regulators of cytoskeleton changes