Combined Matrix-Isolation Infrared and Theoretical DFT and ab Initio Study of the Nonionized Valine Conformers

We present results of the first experimental observation of the nonionized natural amino acid valine. The study has employed the matrix-isolation IR spectroscopy and the density functional theory (DFT) and ab initio calculations. In the calculations geometries of nine low-energy valine conformers were optimized using the DFT method with the B3LYP parametrization and the 6-31++G** basis set. Additionally, the relative energies of the conformers were calculated at the MP2/6-31++G** level. The harmonic frequencies and IR intensities were calculated for all the minima found. These data were used to separate and assign the bands of the valine conformers in the experimental spectra. We found that two valine conformers are present in the Ar matrix: one with a bifurcated NH 2 ‚‚‚OdC H-bond (conformer Ia) and one with a N‚‚‚H-O H-bond (conformer IIa). A trace amount of a third valine conformer with NH 2 ‚‚‚O-C H-bond (conformer IIIb) was also detected. The conformational composition of the matrix-deposited nonionized valine was determined on the basis of observed and predicted IR intensities of the bands of different conformers. The composition is ∼94% of conformer Ia, ∼5% of conformer IIa, and less than 2% of conformer IIIb. The presence of three valine conformers in the Ar matrix results in broadening and/or in multiplex structures of some bands in the valine IR spectrum. Common features in the IR spectra of some nonionized natural aliphatic amino acids are discussed

Foldamers of β-peptides : conformational preference of peptides formed by rigid building blocks : The first MI-IR spectra of a triamide nanosystem

To determine local chirality driven conformational preferences of small aminocyclobutane-1-carboxylic acid derivatives, X-(ACBA) n -Y, their matrix-isolation IR spectra were recorded and analyzed. For the very first time model systems of this kind were deposited in a frozen (~10 K) noble gas matrix to reduce line width and thus, the recorded sharp vibrational lines were analyzed in details. For cis-(S,R)-1 monomer two “zigzag” conformers composed of either a six or an eight-membered H-bonded pseudo ring was identified. For trans-(S,S)-2 stereoisomer a zigzag of an eight-membered pseudo ring and a helical building unit were determined. Both findings are fully consistent with our computational results, even though the relative conformational ratios were found to vary with respect to measurements. For the dimers (S,R,S,S)-3 and (S,S,S,R)-4 as many as four different cis,trans and three different trans,cis conformers were localized in their matrix-isolation IR (MI-IR) spectra. These foldamers not only agree with the previous computational and NMR results, but also unambiguously show for the first time the presence of a structure made of a cis,trans conformer which links a “zigzag” and a helical foldamer via a bifurcated H-bond. The present work underlines the importance of MI-IR spectroscopy, applied for the first time for triamides to analyze the conformational pool of small biomolecules. We have shown that the local chirality of a β-amino acid can fully control its backbone folding preferences. Unlike proteogenic α-peptides, β- and especially (ACBA) n type oligopeptides could thus be used to rationally design and influence foldamer’s structural preferences

SBS 1150+599A: an extremely oxygen-poor planetary nebula in the Galactic halo?

We report results of a spectrophotometric study of SBS 1150+599A and discuss the nature of this object based upon our data. Our study shows that SBS 1150+599A is most probably a planetary nebula located in the Galactic halo and not a cataclysmic variable as originally proposed by the authors of the Second Byurakan Survey from low resolution spectroscopy. We have further elaborated on the properties of SBS 1150+599A (now becoming PN G135.9+55.9) with tools used for planetary nebula analysis. Our photoionization models show that, in order to match the observational constraints, the oxygen abundance in the nebula is probably extremely low, around 1/500 solar, which is one order of magnitude lower than the most oxygen-poor planetary nebulae known so far. This finding has strong implications on our understanding of the formation of planetary nebulae and of the evolution of the Galactic halo.Comment: 13 pages, 5 figures, accepted for publication in Astronomy and Astrophysic

Matrix-Isolation Infrared and Theoretical Studies of the Glycine Conformers

The IR spectra of nonionized glycine and its deuterated derivatives isolated in the low-temperature argon matrices have been measured, and for the first time the infrared spectral characteristics of the three most stable conformers have been determined and assigned. Correlated level ab initio and density functional theory (DFT) calculations of IR frequencies and intensities with extended basis sets were performed and their results were employed to separate the bands of the glycine conformers in the experimental spectra and to assist the assignment. The intramolecular interconversion, conformer III w conformer I, which is observed in the matrices at temperatures higher than 13 K, was found to cause a significant decrease of the band intensities of conformer III in the spectra. This phenomenon was used to distinguish the vibrational bands of this conformer from the bands of the other conformers. The reliability of the Møller-Plesset second-order perturbation theory (MP2) method and the DFT method with the three-parameter density functional, Becke3LYP, in the prediction of the IR spectra of the nonionized glycine conformers was examined. We found that the DFT/Becke3LYP method with aug-cc-pVDZ basis set yields vibrational frequencies of the glycine conformers very similar to the MP2 results. Both DFT and MP2 results are in the excellent agreement with the experimental data

The Second Byurakan Survey Galaxies. I. The Optical Database

A database for the entire catalog of the Second Byurakan Survey (SBS) galaxies is presented. It contains new measurements of their optical parameters and additional information taken from the literature and other databases. The measurements were made using Ipg(near-infrared), Fpg(red) and Jpg(blue) band images from photographic sky survey plates obtained by the Palomar Schmidt telescope and extracted from the STScI Digital Sky Survey (DSS). The database provides accurate coordinates, morphological type, spectral and activity classes, apparent magnitudes and diameters, axial ratios, and position angles, as well as number counts of neighboring objects in a circle of radius 50 kpc. The total number of individual SBS objects in the database is now 1676. The 188 Markarian galaxies which were re-discovered by SBS are not included in this database. We also include redshifts that are now available for 1576 SBS objects, as well as 2MASS infrared magnitudes for 1117 SBS galaxies.Comment: 13 pages, 1 figure, 1 tabl

Very-high-energy gamma radiation associated with the unshocked wind of the Crab pulsar

We show that the relativistic wind in the Crab pulsar, which is commonly thought to be invisible in the region upstream of the termination shock at R < 0.1 pc, in fact could be directly observed through its inverse Compton gamm-ray emission. The search for such specific component of radiation in the gamma-ray spectrum of the Crab can provide unique information about the unshocked pulsar wind that is not accessible at other wavelengths.Comment: 11 pages, 11 figures, to appear in one of the April issues of MNRA

Physical parameters and classification of eight galactic nuclei from the Second Byurakan Survey

Spectroscopic observations with a resolution of 4.5 Angst were performed for a sample of eight galactic nuclei extracted from the Second Byurakan Survey, and one companion galaxy of SBS 1204+505B. The EW and FWHM of the emission lines were measured, and useful line ratios and diagnostic diagrams were used for object classification and reddening estimates. Intrinsic reddening quantities were calculated for all non QSO,i.e. seven objects. Particularly the amount of reddening, BV color excess, extinction coefficient and optical depths in the V band, at Halpha and Hbeta wavelengths, and at 5100 Angst. The broad line region size was also estimated for seven objects, as well as the central black hole masses. Three mass estimates were usually performed for each object and compared. A peculiar line, probably He I lambda 5048, is detected in the QSO SBS 1626+554. Evidence for a stratified narrow line region is found for the two narrow line Seyfert 1 galaxies included in the sample. A revised classification is proposed for two objects, and the companion galaxy of SBS 1204+505B is reported as a nuclear starburst galaxy.Comment: To appear in PAS

The Sloan Digital Sky Survey Reverberation Mapping Project: Rapid CIV Broad Absorption Line Variability

We report the discovery of rapid variations of a high-velocity CIV broad absorption line trough in the quasar SDSS J141007.74+541203.3. This object was intensively observed in 2014 as a part of the Sloan Digital Sky Survey Reverberation Mapping Project, during which 32 epochs of spectroscopy were obtained with the Baryon Oscillation Spectroscopic Survey spectrograph. We observe significant (>4sigma) variability in the equivalent width of the broad (~4000 km/s wide) CIV trough on rest-frame timescales as short as 1.20 days (~29 hours), the shortest broad absorption line variability timescale yet reported. The equivalent width varied by ~10% on these short timescales, and by about a factor of two over the duration of the campaign. We evaluate several potential causes of the variability, concluding that the most likely cause is a rapid response to changes in the incident ionizing continuum. If the outflow is at a radius where the recombination rate is higher than the ionization rate, the timescale of variability places a lower limit on the density of the absorbing gas of n_e > 3.9 x 10^5 cm^-3. The broad absorption line variability characteristics of this quasar are consistent with those observed in previous studies of quasars, indicating that such short-term variability may in fact be common and thus can be used to learn about outflow characteristics and contributions to quasar/host-galaxy feedback scenarios.Comment: 15 pages, 14 figures. Accepted for publication in the Astrophysical Journa

The Hamburg/SAO survey for low metallicity blue compact/HII-galaxies (HSS-LM). I. The first list of 46 strong-lined galaxies

We present the description and the first results of a new project devoted to the search for extremely metal-deficient blue compact/HII-galaxies (BCGs) and to the creation of a well selected large BCG sample with strong emission lines. Such galaxies should be suitable for reliable determination of their oxygen abundance through the measurement of the faint [OIII]4363A line. The goals of the project are two-fold: a) to discover a significant number of new extremely metal-poor galaxies (Z <= 1/20 Zo), and b) to study the metallicity distribution of local BCGs. Selection of candidates for follow-up slit spectroscopy is performed on the database of objective prism spectra of the Hamburg Quasar Survey. The sky region is limited by delta >= 0 deg. and b^ii <= -30 deg. In this paper we present the results of the follow-up spectroscopy conducted with the Russian 6m telescope. The list of observed candidates contained 52 objects, of which 46 were confirmed as strong-lined BCGs (EW([OIII]5007) >= 100 A). The remaining five lower excitation ELGs include three BCGs, and two galaxies classified as SBN (Starburst Nucleus) and DANS (Dwarf Amorphous Nucleus Starburst). One object is identified as a quasar with a strong Ly_alpha emission line near 5000 A (z~3). We provide a list with coordinates, measured radial velocities, B-magnitudes, equivalent widths EW([OIII]5007) and EW(H_beta) and for the 46 strong-lined BCGs the derived oxygen abundances 12+log(O/H). The abundances range between 7.42 and 8.4 (corresponding to metallicities between 1/30 and 1/3 Zo). The sample contains four galaxies with Z < 1/20 Zo, of which three are new discoveries.Comment: 19 pages, 13 figures, accepted for publication in A&A, corrected typos, reference