Radiation-driven hydrodynamics of high- hohlraums on the national ignition facility

The first hohlraum experiments on the National Ignition Facility (NIF) using the initial four laser beams tested radiation temperature limits imposed by plasma filling. For a variety of hohlraum sizes and pulse lengths, the measured x-ray flux shows signatures of filling that coincide with hard x-ray emission from plasma streaming out of the hohlraum. These observations agree with hydrodynamic simulations and with an analytical model that includes hydrodynamic and coronal radiative losses. The modeling predicts radiation temperature limits with full NIF (1.8 MJ), greater, and of longer duration than required for ignition hohlraums.     

Electronic control of chiral quaternary center creation in the intramolecular asymmetric heck reaction

The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.     

Buffer-gas cooling of NH via the beam loaded buffer-gas method

NH radicals from a molecular beam are cooled using a novel beam-loaded buffer gas method. The radicals are produced in a glow discharge beam source and injected into cryogenic helium gas. Up to 10¹² molecules in their ground electronic, vibrational, and rotational state are detected in the buffer gas and translational temperatures under 6 K are achieved. The cooling method presented is general and can be applied to any molecules in a molecular beam.Received: 20 July 2004, Published online: 26 October 2004PACS: 33.80.Ps Optical cooling of molecules; trapping - 34.50.Ez Rotational and vibrational energy transfer - 39.10. + j Atomic and molecular beam sources and techniquesB. Friedrich: Present address: Department of Molecular Physics, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany.     

Using a dual inlet atmospheric pressure ionization source as a dynamic reaction vessel

Atmospheric pressure ionization (API) sources have the ability to serve as dynamic 'reaction vessels' and this capability has been rapidly evolving over the past few years. With API sources, many different reagents and source conditions can be rapidly explored with minimal carryover or contamination of the mass spectrometer. While most API applications involve the simple protonation/deprotonation of analyte molecules, a great deal of flexibility and utility is available in almost any API source, provided the reagents and ionization conditions are judiciously selected. Here, the generation of a unique and useful class of reagent ions at atmospheric pressure is demonstrated for the first time. Within the AP gas-phase environment of a dual inlet ion source, the gas-phase synthesis of substituted N-phenylpyridinium cations is demonstrated by establishing conditions favorable to the nucleophilic substitution reaction required for their formation. The flexibility of this API source as a reaction vessel is also demonstrated.     

Some new methods for preparing 2,3- and 3,4-diaminopyridines

New methods of preparing 2,3-diaminopyridine ( 13 ) from 2-chloro-3-nitropyridine ( 11 ) and 3,4-diaminopy-ridine ( 8 ) from 4-ethoxy-3-nitropyridine hydrochloride ( 5 ) have been explored and evaluated.     

The Index of an Infinite Dimensional Implicit System

The idea of the index of a differential algebraic equation (DAE) (or implicit differential equation) has played a fundamental role in both the analysis of DAEs and the development of numerical algorithms for DAEs. DAEs frequently arise as partial discretizations of partial differential equations (PDEs). In order to relate properties of the PDE to those of the resulting DAE it is necessary to have a concept of the index of a possibly constrained PDE. Using the finite dimensional theory as motivation, this paper will examine what one appropriate analogue is for infinite dimensional systems. A general definition approach will be given motivated by the desire to consider numerical methods. Specific examples illustrating several kinds of behavior will be considered in some detail. It is seen that our definition differs from purely algebraic definitions. Numerical solutions, and simulation difficulties, can be misinterpreted if this index information is missing.     

Radiotracer studies of the antitumor metallocene molybdocene dichloride with biomolecules

Neutron irradiation of Cp₂MoCl₂ for 24 h afforded the radiotracer Cp₂⁹⁹MoCl₂ which was characterised by UV–Vis spectroscopy and thin layer chromatography. Binding experiments with the thiol containing protein human serum albumin (HSA) or calf thymus DNA, were monitored for ⁹⁹Mo using a gamma counter. Under the conditions investigated, molar ratios of binding of 0.2:1 (Cp₂MoCl₂:DNA) and 9.4:1 (Cp₂MoCl₂:HSA) were calculated. The results are consistent with in vitro coordination studies that have shown strong preferential interaction of Cp₂MoCl₂ with thiols versus other donor sites in biomolecules including DNA.     

Reduced occupancy of the deeply bound 0d(5/2) neutron state in 32Ar

The 9Be(32Ar, 31Ar)X reaction, leading to the 5/2+ ground state of a nucleus at the proton drip line, has a cross section of 10.4(13) mb at a beam energy of 65.1 MeV/nucleon. This translates into a spectroscopic factor that is only 24(3)% of that predicted by the many-body shell-model theory. We introduce refinements to the eikonal reaction theory used to extract the spectroscopic factor to clarify that this very strong reduction represents an effect of nuclear structure. We suggest that it reflects correlation effects linked to the high neutron separation energy (22.0 MeV) for this state.