The total synthesis of the crinine alkaloid hamayne via a Pd[0]-catalyzed intramolecular alder-ene reaction

The racemic form of the title alkaloid, 1, has been prepared in 13 steps from the ring-fused gem-dibromocyclopropane 7. Key transformations include the thermally induced electrocyclic ring-opening of compound 7, the Pd[0]-catalyzed intramolecular Alder-ene (IMAE) reaction of the derived sulfonamide (±)-12, and the conversion of the ensuing C-3a-arylhexahydroindole (±)-16 into (±)-hamayne via a Pictet-Spengler reaction.     

A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions

We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a ¹⁵N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process.     

Ultra-low background measurements of decayed aerosol filters

Aerosol samples collected on filter media were analyzed using HPGe detectors employing varying background-reduction techniques in order to experimentally evaluate the opportunity to apply ultra-low background measurement methods to samples collected, for instance, by the Comprehensive Test Ban Treaty International Monitoring System (IMS). In this way, realistic estimates of the impact of low-background methodology on the sensitivity obtained in systems such as the IMS were assessed. The current detectability requirement of stations in the IMS is 30 μBq/m³ of air for ¹⁴⁰Ba, which would imply ~10⁶ fissions per daily sample. Importantly, this is for a fresh aerosol filter. One week of decay reduces the intrinsic background from radon daughters in the sample allowing much higher sensitivity measurement of relevant isotopes, including ¹³¹I. An experiment was conducted in which decayed filter samples were measured at a variety of underground locations using Ultra-Low Background (ULB) gamma spectroscopy technology. The impacts of the decay and ULB are discussed.     

Tunable remote pinning of domain walls in magnetic nanowires

Domain wall (DW) pinning in ferromagnetic nanowires is in general a complex process. Distortions of the DW shape make quantitative agreement between modeling and experiment difficult. Here we demonstrate pinning using nanometer scale localized stray fields. This type of interaction gives well-characterized, tailorable potential landscapes that do not appreciably distort the DW. Our experimental results are in excellent quantitative agreement with an Arrhenius-Néel model of depinning--a result only possible when the modeled potential profile agrees fully with that experienced by the DW.     

Towards factoring in {SL(2,\,\mathbb{F}_{2^n})}

The security of many cryptographic protocols relies on the hardness of some computational problems. Besides discrete logarithm or integer factorization, other problems are regularly proposed as potential hard problems. The factorization problem in finite groups is one of them. Given a finite group G, a set of generators generators for this group and an element ${g\in G}$ , the factorization problem asks for a “short” representation of g as a product of the generators. The problem is related to a famous conjecture of Babai on the diameter of Cayley graphs. It is also motivated by the preimage security of Cayley hash functions, a particular kind of cryptographic hash functions. The problem has been solved for a few particular generator sets, but essentially nothing is known for generic generator sets. In this paper, we make significant steps towards a solution of the factorization problem in the group ${G:=\,SL(2,\,\mathbb{F}_{2^n})}$ , a particularly interesting group for cryptographic applications. To avoid considering all generator sets separately, we first give a new reduction tool that allows focusing on some generator sets with a “nice” special structure. We then identify classes of trapdoor matrices for these special generator sets, such that the factorization of a single one of these matrices would allow efficiently factoring any element in the group. Finally, we provide a heuristic subexponential time algorithm that can compute subexponential length factorizations of any element for any pair of generators of ${SL(2,\,\mathbb{F}_{2^n})}$ . Our results do not yet completely remove the factorization problem in ${SL(2,\,\mathbb{F}_{2^n})}$ from the list of potential hard problems useful for cryptography. However, we believe that each one of our individual results is a significant step towards a polynomial time algorithm for factoring in ${SL(2,\,\mathbb{F}_{2^n})}$ .     

On the hyperfine structure in the configuration 5f 3 6d7s 2 of neutral uranium

A Laser Induced Fluorescence experiment in an atomic beam has yielded experimental values of hyperfine structure (hfs) constants A and B for 28 low odd levels and 22 even levels, with an accuracy around 10^–5 cm^–1 for A and 10^–3 cm^–1 for B. A Condon Slater Racah parametric interpretation of the hfs data concerning 22 of these levels, on the basis of the configuration 5f ³ 6d 7s ², has provided values of monoelectronic parametersa _5f ⁰¹ ,a _5f ¹² ,a _6d ⁰¹ ,b _5f ⁰² ,b _6d ⁰² ,b _6d ¹³ . A least square fit calculation has been compared to the values deduced from Dirac-Fock monoelectronic radial integrals. The fit represents 18 A (16 B) values ranging from –0.42 to –2.96 mK (from –41 to 156 mK) with discrepancies less than 0.2 mK (8 mK).     

Investigation of the microporosity of high performance concrete by proton nuclear relaxation.

The difference in microporosity features between high and ultra high performance concrete was highlighted by measuring their respective proton spin-lattice relaxation times. A surface fractal dimension was attributed to each formulation and exhibits a correlation with the amount of calcium silicate hydrates.     

Buffeting in transonic flow prediction using time‐dependent turbulence model

In transonic flow conditions, the shock wave/turbulent boundary layer interaction and flow separations on wing upper surface induce flow instabilities, ‘buffet’, and then the buffeting (structure vibrations). This phenomenon can greatly influence the aerodynamic performance. These flow excitations are self‐sustained and lead to a surface effort due to pressure fluctuations. They can produce enough energy to excite the structure. The objective of the present work is to predict this unsteady phenomenon correctly by using unsteady Navier–Stokes‐averaged equations with a time‐dependent turbulence model based on the suitable (k–ε) turbulent eddy viscosity model. The model used is based on the turbulent viscosity concept where the turbulent viscosity coefficient (Cμ) is related to local deformation and rotation rates. To validate this model, flow over a flat plate at Mach number of 0.6 is first computed, then the flow around a NACA0012 airfoil. The comparison with the analytical and experimental results shows a good agreement. The ONERA OAT15A transonic airfoil was chosen to describe buffeting phenomena. Numerical simulations are done by using a Navier–Stokes SUPG (streamline upwind Petrov–Galerkin) finite‐element solver. Computational results show the ability of the present model to predict physical phenomena of the flow oscillations. The unsteady shock wave/boundary layer interaction is described. Copyright © 2005 John Wiley & Sons, Ltd.