Functionalization of saturated hydrocarbons. High temperature bromination of octahydropentalene. Part 19

The synthesis and thermal bromination of octahydropentalene was studied. The reaction afforded 1a,3a,4b,6b-tetrabromo-1,2,3,4,5,6-hexahydropentalene (14) with remarkable regio- and stereospecificity. The structure of the product was determined by ¹H and ¹³C NMR data and single X-ray structural analysis. The treatment of octahydropentalene with tenfold bromine gave the octabromopentalene derivative. The formation mechanism of the products is discussed.     

Natural abundance 13C - 13C coupling constants observed via double quantum coherence. Structural elucidation by the one- and the two-dimensional NMR experiements of velloziolone,a new seco-diterpene.

With the help of Natural Abundance ¹³C - ¹³C Coupling Constants, observed via double quantum coherence, the structural determination of VELLOZIOLONE (1), a new diterpene, has been carried out.     

Gas-phase ion/molecule reactions between dimethoxyphosphonium ions and aromatic hydrocarbons

Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described.     

Direct quantitative analysis of peptides using matrix assisted laser desorption ionization

The protocol and various matrices were examined for quantification of biomolecules in both the low ca. 1200 amu and mid mass 6000-12000 amu ranges using an internal standard. Comparative studies of different matrices of MALDI quantitative analysis showed that the best accuracy and standard curve linearity were obtained for two matrices: (a) 2,5-dihydroxybenzoic acid (DHB) combined with a comatrix of fucose and 5-methoxysalicylic acid (MSA) and (b) ferulic acid/fucose. In the low mass range, the quantitative limit was in the 30 fmol range and in the mid mass range the quantitative limit was in the 250 fmol range. Linear response was observed over 2-3 decades of analyte concentration. The relative error of the standard curve slope was 1.3-1.8% with correlation coefficients of 0.996-0.998.The main problem for quantitative measurement was suppression of the signal of the less concentrated component (analyte or internal standard) by the more concentrated component. The effect was identified with saturation of the matrix by the analyte. The threshold of matrix saturation was found to be in the range of 1/(3000-5000) analyte/matrix molar ratio. To avoid matrix saturation the (analyte+internal standard) to matrix molar ratio should be below this threshold. Thus the internal standard concentration should be as low as possible.DHB/MSA/fucose and ferulic acid/fucose matrices demonstrated good accuracy and linearity for standard curves even when the internal standard had chemical properties different from the analyte. However, use of an internal standard with different chemical properties requires highly stable instrumental parameters as well as constant (analyte+internal standard)/matrix molar ratio for all samples.     

Bacterial Reduction of Chromium

A mixed culture was enriched from surface soil obtained from an eastern United States site highly contaminated with chromate. Growth of the culture was inhibited by a chromium concentration of 12 mg/L. Another mixed culture was enriched from subsurface soil obtained from the Hanford reservation, at the fringe of a chromate plume. The enrichment medium was minimal salts solution augmented with acetate as the carbon source, nitrate as the terminal electron acceptor, and various levels of chromate. This mixed culture exhibited chromate tolerance, but not chromate reduction capability, when growing anaerobically on this medium. However, this culture did exhibit chromate reduction capability when growing anaerobically on TSB. Growth of this culture was not inhibited by a chromium concentration of 12 mg/L. Mixed cultures exhibited decreasing diversity with increasing levels of chromate in the enrichment medium. An in situ bioremediation strategy is suggested for chromate contaminated soil and groundwater.

     

Coordinating California’s efforts to promote waste to alcohol production

Alcohol fuels produced from biomass can improve air quality, enhance energy security, create employment opportunities, and reduce waste disposal problems. Opportunities in California exist to produce alcohols from waste streams from various sectors of the economy. Government agencies have promoted waste-to-alcohol activities, but efforts have been inconsistent and intermittent. Often these efforts have been hindered by contradictory but mandate-driven policies. A prudent approach to coordinate statewide efforts includes the development of an integrated statewide policy to examine barriers that impede private sector business efforts to produce alcohols from biomass. A multi-agency task force to promote research, development, commercialization, and marketing efforts for biomass-produced alcohols is desirable. The views and opinions contained in this document do not necessarily reflect those of the California Energy Commission, its staff, management, or the State of California.     

Correlation between Site ll-Specific Human Serum Albumin (HSA) Binding Affinity and Murine in vivo Photosensitizing Efficacy of Some Photofrin Components

Human serum albumin (HSA) is one of the key components in human blood that may influence drug distribution. As such, it is important to know the affinity of any drug for albumin. Previously, Photofrina mixture of monomeric, dimeric and oligomeric porphyrins, has been subjected to HSA binding studies. However, due to its complex nature, binding studies on Photofrin or other hematoporphyrin derivatives with HSA are inconclusive. In this report, the binding properties of some components (dimers and trimers) of Photofrin® and the relationship between murine photosensitizing efficacy and those binding properties were investigated. The interaction of these porphyrins with HSA was investigated by direct ultrafiltration and fluorescent titration techniques with fluorescent probes such as dansyl-L-proline (DP), which is known to interact selectively with site II on HSA. Porphyrins also were tested for antitumor activity in a mouse model following intravenous administration and exposure to laser light. Together, the results suggest that the photosensitizers that were preferentially bound to site II of HSA were most effective at controlling murine tumor regrowth