Electron capture dissociation and infrared multiphoton dissociation of oligodeoxynucleotide dications

We report electron capture dissociation (ECD) and infrared multiphoton dissociation (IRMPD) of doubly protonated and protonated/alkali metal ionized oligodeoxynucleotides. Mass spectra following ECD of the homodeoxynucleotides polydC, polydG, and polydA contain w or d "sequence" ions. For polydC and polydA, the observed fragments are even-electron ions, whereas radical w/d ions are observed for polydG. Base loss is seen for polydG and polydA but is a minor fragmentation pathway in ECD of polydC. We also observe fragment ions corresponding to w/d plus water in the spectra of polydC and d(GCATGC). Although the structure of these ions is not clear, they are suggested to proceed through a pentavalent phosphorane intermediate. The major fragment in ECD of d(GCATGC) is a d ion. Radical a- or z-type fragment ions are observed in most cases. IRMPD primarily results in base loss, but backbone fragmentation is also observed. IRMPD provides more sequence information than ECD, but the spectra are more complex due to extensive base and water losses. It is proposed that the smaller degree of sequence coverage in ECD, with fragmentation mostly occurring close to the ends of the molecules, is a consequence of a mechanism in which the electron is captured at a P=O bond, resulting in a negatively charged phosphate group. Consequently, at least two protons (or alkali metal cations) must be present to observe a w or d fragment ion, a requirement that is less likely for small fragments.     

Dissolved urate salts out calcium oxalate in undiluted human urine in vitro: implications for calcium oxalate stone genesis

Hyperuricosuria has long been documented as a predisposing factor to calcium oxalate (CaOx) stone pathogenesis. However, its mechanism is still without sound scientific foundation. Previously, we showed that hyperuricosuria, simulated by the addition of dissolved sodium urate, promotes the crystallization of CaOx. In the present study, we demonstrate that the urate's effect on the crystallization is attributable to its salting out CaOx from solution. Furthermore, analysis of urines revealed that their metastable limit decreased with increases in the product of the prevailing concentrations of calcium and urate: this has implications for CaOx stone genesis. We also outline anti-salting out strategies for future research for the prevention and/or treatment of CaOx calculi.     

Synthesis of 2,5-disubstituted tetrahydrofurans by stereospecific elimination-cyclization of 1-iodomethyl-1,5-bis-epoxides

[reaction: see text] Treatment of 1-iodomethyl-1,5-bis-epoxides with zinc in refluxing ethanol affords cis or trans 2-vinyl-5-(1-hydroxyethy)-substituted tetrahydrofurans stereospecifically in high yield.     

Reporter resins for solid-phase chemistry

[reaction: see text] An analytical construct resin, designed to aid the analysis of solid-phase chemistry, has been mixed in a small proportion with a conventional resin. The analytical construct ("reporter resin") contains two orthogonal linkers that allow cleavage of either the synthetic intermediates (at linker 2) or their analytically enhanced derivatives (at linker 1). The convenient and rapid monitoring of each step in the syntheses of representative library compounds was possible using small resin aliquots.     

Measurement of the resonant d(mu)t molecular formation rate in solid HD

Measurements of muon-catalyzed dt fusion ( d(mu)t-->4He + n + mu(-)) in solid HD have been performed. The theory describing the energy dependent resonant molecular formation rate for the reaction (mu)t + HD-->[(d(mu)t)pee](*) is compared to experimental results in a pure solid HD target. Constraints on the rates are inferred through the use of a Monte Carlo model developed specifically for the experiment. From the time-of-flight analysis of fusion events in 16 and 37 microg x cm(-2) targets, an average formation rate consistent with 0.897+/-(0.046)(stat)+/-(0.166)(syst) times the theoretical prediction was obtained.     

New uniqueness theorems for trigonometric series

A uniqueness theorem is proved for trigonometric series and another one is proved for multiple trigonometric series. A corollary of the second theorem asserts that there are two subsets of the -dimensional torus, the first having a countable number of points and the second having points such that whenever a multiple trigonometric series ``converges' to zero at each point of the former set and also converges absolutely at each point of the latter set, then that series must have every coefficient equal to zero. This result remains true if ``converges' is interpreted as any of the usual modes of convergence, for example as ``square converges' or as ``spherically converges.'

     

Progress in direct-drive inertial confinement fusion research at the laboratory for laser energetics

Direct-drive inertial confinement fusion (ICF) is expected to demonstrate high gain on the National Ignition Facility (NIF) in the next decade and is a leading candidate for inertial fusion energy production. The demonstration of high areal densities in hydrodynamically scaled cryogenic DT or D₂ implosions with neutron yields that are a significant fraction of the “clean” 1-D predictions will validate the ignition-equivalent direct-drive target performance on the OMEGA laser at the Laboratory for Laser Energetics (LLE). This paper highlights the recent experimental and theoretical progress leading toward achieving this validation in the next few years. The NIF will initially be configured for X-ray drive and with no beams placed at the target equator to provide a symmetric irradiation of a direct-drive capsule. LLE is developing the “polar-direct-drive” (PDD) approach that repoints beams toward the target equator. Initial 2-D simulations have shown ignition. A unique “Saturn-like” plastic ring around the equator refracts the laser light incident near the equator toward the target, improving the drive uniformity. LLE is currently constructing the multibeam, 2.6-kJ/beam, petawatt laser system OMEGA EP. Integrated fast-ignition experiments, combining the OMEGA EP and OMEGA Laser Systems, will begin in FY08.