Genomic Analysis of the Hydrocarbon-Producing, Cellulolytic, Endophytic Fungus Ascocoryne sarcoides

The microbial conversion of solid cellulosic biomass to liquid biofuels may provide a renewable energy source for transportation fuels. Endophytes represent a promising group of organisms, as they are a mostly untapped reservoir of metabolic diversity. They are often able to degrade cellulose, and they can produce an extraordinary diversity of metabolites. The filamentous fungal endophyte Ascocoryne sarcoides was shown to produce potential-biofuel metabolites when grown on a cellulose-based medium; however, the genetic pathways needed for this production are unknown and the lack of genetic tools makes traditional reverse genetics difficult. We present the genomic characterization of A. sarcoides and use transcriptomic and metabolomic data to describe the genes involved in cellulose degradation and to provide hypotheses for the biofuel production pathways. In total, almost 80 biosynthetic clusters were identified, including several previously found only in plants. Additionally, many transcriptionally active regions outside of genes showed condition-specific expression, offering more evidence for the role of long non-coding RNA in gene regulation. This is one of the highest quality fungal genomes and, to our knowledge, the only thoroughly annotated and transcriptionally profiled fungal endophyte genome currently available. The analyses and datasets contribute to the study of cellulose degradation and biofuel production and provide the genomic foundation for the study of a model endophyte system

Synthesis, Structure, and Thermochemistry of the Formation of the Metal−Metal Bonded Dimers [Mo(μ-TeAr)(CO)3(PiP3)]2 (Ar = Phenyl, Naphthyl) by Phosphine Elimination from •Mo(TePh)(CO)3(PiPr3)2

The complexes (•TeAr)Mo(CO)3(PiPr3)2 (Ar = phenyl, naphthyl; iPr = isopropyl) slowly eliminate PiPr3 at room temperature in a toluene solution to quantitatively form the dinuclear complexes [Mo(μ-TeAr)(CO)3(PiPr3)]2. The crystal structure of [Mo(μ-Te−naphthyl)(CO)3(PiPr3)]2 is reported and has a Mo−Mo distance of 3.2130 Å. The enthalpy of dimerization has been measured and is used to estimate a Mo−Mo bond strength on the order of 30 kcal mol-1. Kinetic studies show the rate of formation of the dimeric chalcogen bridged complex is best fit by a rate law first order in (•TeAr)Mo(CO)3(PiPr3)2 and inhibited by added PiPr3. The reaction is proposed to occur by initial dissociation of a phosphine ligand and not by radical recombination of 2 mol of (•TeAr)Mo(CO)3(PiPr3)2. Reaction of (•TePh)Mo(CO)3(PiPr3)2, with L = pyridine (py) or CO, is rapid and quantitative at room temperature to form PhTeTePh and Mo(L)(CO)3(PiPr3)2, in keeping with thermochemical predictions. The rate of reaction of (•TeAr)W(CO)3(PiPr3)2 and CO is first-order in the metal complex and is proposed to proceed by the associative formation of the 19 e- radical complex (•TePh)W(CO)4(PiPr3)2 which extrudes a •TePh radical

PERTURBATIONS AND VIBRATIONAL ENERGIES IN ACRYLONITRILE FROM GLOBAL ANALYSIS OF ITS MM-WAVE TO THZ ROTATIONAL SPECTRUM

Author Institution: Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warszawa, Poland; Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, CA 91109-8099, USA; Department of Physics, Wright State University, Dayton, OH 45435, USA; Department of Physics, The Ohio State University, Columbus, OH 43210, USAThe rotational spectrum of acrylonitrile has recently been studied in some detail up to THz frequencies., {\bf 258}, 26 (2009).}$^,$, {\bf 1006}, 20 (2011).} The perturbation between the ground state and $v_{11}=1$ that was initially identified in the parent$^a$ has also been observed in other isotopologues.$^b$ The considerable energy difference between these states (228.29991(2) cm$^{-1}$ in the parent) was, in all cases, determined entirely from perturbations in rotational transitions. \vspace{0.2cm} Many other perturbations in rotational transitions have been identified, allowing the $v_{15}=1$ level to be added to the analysis., MH09, 66th OSU International Symposium on Molecular Spectroscopy (2011)} We have now extended the broadband coverage of the rotational spectrum even further, and have been able to add the fourth vibrational state, $v_{11}$=2, to the global analysis. The current coupled fit encompasses well over 12000 transition frequencies and delivers precise vibrational energy information entirely on the basis of many fitted perturbations in rotational transitions. The present work was used to further refine the features for identifying perturbations built into the AABS package for Assignment and Analysis of Broadband Spectra., {\bf 233}, 231 (2005).