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At least 217 records · Page 12

Enhanced Isomer Population via Direct Irradiation of Solid-Density Targets Using a Compact Laser-Plasma Accelerator

Excitation of long-lived states in bromine nuclei using a tabletop laser-plasma accelerator providing pulsed (<100 fs) electron beams provided a sensitive probe of γ strength and level densities in the nuclear quasicontinuum and may indicate angular momentum coupling through electron-nuclear interactions. Solid-density active $LaBr_{3}$ targets absorb real and virtual photons up to 35 ± 2.5 MeV and deexcite through γ cascade into different states. Here, a factor of 4.354 ± 0.932 enhancement of the $^{80}Br^{m}/^{80}Br^{g}$ isomeric ratio was observed following electron irradiation, as compared to bremsstrahlung. Additional angular momentum transfer could possibly occur through nuclear-plasma or electron-nuclear interactions enabled by the ultrashort electron beam. Further investigation of these mechanisms could have far-reaching impact including decreased storage of long-term nuclear waste and an improved understanding of heavy element formation in astrophysical settings.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Stereoinversion via Alcohol Dehydrogenases Enables Complete Catabolism of β-1-Type Lignin-Derived Aromatic Isomers

Sphingobium sp. strain SYK-6 is an efficient aromatic catabolic bacterium that can consume all four stereoisomers of 1,2-diguaiacylpropane-1,3-diol (DGPD), which is a ring-opened β-1-type dimer. Recently, LdpA-mediated catabolism of erythro-DGPD was reported in SYK-6, but the catabolic pathway for threo-DGPD was as yet unknown. Here, in this study, we elucidated the catabolism of threo-DGPD, which proceeds through conversion to erythro-DGPD. When threo-DGPD was incubated with SYK-6, the Cα hydroxy groups of threo-DGPD (DGPD I and II) were initially oxidized to produce the Cα carbonyl form (DGPD-keto I and II). This initial oxidation step is catalyzed by Cα-dehydrogenases, which belong to the short-chain dehydrogenase/reductase (SDR) family and are involved in the catabolism of β-O-4-type dimers. Analysis of seven candidate genes revealed that NAD + -dependent LigD and LigL are mainly involved in the conversion of DGPD I and II, respectively. Next, we found that DGPD-keto I and II were reduced to erythro-DGPD (DGPD III and IV) in the presence of NADPH. Genes involved in this reduction were sought from Cα-dehydrogenase and ldpA-neighboring SDR genes. The gene products of SLG_12690 (ldpC) and SLG_12640 (ldpB) catalyzed the NADPH-dependent conversion of DGPD-keto I to DGPD III and DGPD-keto II to DGPD IV, respectively. Mutational analysis further indicated that ldpC and ldpB are predominantly involved in the reduction of DGPD-keto. Together, these results demonstrate that SYK-6 harbors a comprehensive catabolic enzyme system to utilize all four β-1-type stereoisomers through successive oxidation and reduction reactions of the Cα hydroxy group of threo-DGPD with a net stereoinversion using multiple dehydrogenases.

09 BIOMASS FUELS↗

Isomers and Dark Matter: 180m Ta and 178m Hf [Slides]

Dark matter has attractive gravitational interactions. It does not interact with light, or has very small electromagnetic coupling. It is stable, or has a lifetime much longer than the age of the Universe. No departure model from the law of gravity explains all data, whereas particle dark matter can.

79 ASTRONOMY AND ASTROPHYSICS↗

Isomer effects on polyimide properties

The polymerization of 2,4'-methylene-dianiline with benzophenone tetracarboxylic acid dianhydride yields high molecular weight polyamic acid. Polyimide is formed when films of the polyamic acid are cured between 200 - 300 C. A lower molecular weight polyamic acid is obtained from 2,2'-MDA with BTDA, but it appears that a lowering of the reaction temperature will yield high molecular weight polymer. Evaluation of these polymers is underway. Continued efforts to synthesize 2,3'- MDA and 2,3'-diaminobenzophenone have met with little success.

Stump, B. L.↗

Isomer effects on polyimide properties

The effect of structure variation on the solubility and glass-transition temperature of polyimide polymers is investigated. The addition of alkyl substituents to an aromatic ring in the polymer molecule, the reduction in the number of imide rings per average polymer chain-length, and a variation in the symmetry of the polymer molecule are studied. The synthesis of key intermediates for the preparation of the monomers required in this investigation is reported along with progress made in the synthesis of polyimide-precursor amines that contain functional groups to allow for post-cure cross-linking.

Stump, B. L.↗

Isomer effects on polyimide properties

Polyimide polymers which are thermally stable and processable are developed. The addition of alkyl substituents to an aromatic ring in the polymer backbone is examined along with polyimide precursor amines containing functional groups that allow for post-cure crosslinking. The synthesis of key monomers is reported, including 2,4,6-tris (m-aminobenzyl) 1,3,5-trimethyl benzene and 2,4,6-tris (p-aminobenzyl) 1,3,5-trimethyl benzene. The preparation of a key monomer, 2,5,3-triamino benzophenone, is reported.

Stump, B. L.↗

Isomer effects on polyimide properties

Thermally stable polyimide polymers were prepared. Parameters explored include asymmetry of substitution, addition of alkyl substituents to an aromatic ring, and an increase in the number of aromatic rings present in the diamine monomer. It is shown that the use of an asymmetrical diamine in the preparation of a polyimide produces a polymer with a markedly lowered glass transition temperature. This is achieved with little or no sacrifice of thermal stability. An alternate approach taken was to prepare imide monomers which are capable of addition-type polymerization.

Stump, B. L.↗

An explanation of the preferential formation of less stable isomers in three-body reactions - Cl + NO2 + M; ClO + NO2 + M

A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.

Chang, J. S.↗

The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

Lindh, Roland↗