Diastereoselective total synthesis of (+)-13-stemarene by fourth generation methods: a formal total synthesis of (+)-18-deoxystemarin

The problem of constructing diastereoselectively the C/D ring system of stemarane diterpenes from a bicyclo[2.2.2]octane intermediate was solved resulting in very simple synthesis of (+)-13-stemarene 1. The obtaining of the latter represents also a formal synthesis of (+)-18-deoxystemarin 2. In the key step, the epimeric mixture 10, dissolved in toluene, was converted by the action of TsOH into (+)-stemar-13-en-15-one 28.     

Integrated NMR and computational study of push-pull NLO probes: interplay of solvent and structural effects

In this study we combined QM calculations and NMR measurements to understand at a detailed level the complex interplay of structural/electronic properties with the effects of the solvent in the NLO activity of push-pull systems, quantified in terms of variations of the static hyperpolarizability. Different parameters (bond lengths and bond length alternation, vibrational frequencies, electronic charge distribution) are introduced and tested to rationalize both the solvent sensitivity of three molecular systems (namely, p-nitroaniline, ethyl 4-ammino benzoate, and 5-nitro-1H-indole) and the differences among them. This analysis has finally allowed us to establish a clear correlation between the charge transfer behavior of the systems, their NLO properties, and NMR parameters also validating simplified but effective chemical analyses based on resonance limit forms.     

Thiazole orange (TO) as a light-switch probe: a combined quantum-mechanical and spectroscopic study

A Density Functional Theory (DFT) study of the absorbance and fluorescence emission characteristics of the cyanine thiazole orange (TO) in solution and when intercalated in DNA was carried out in combination with spectrophotometric and spectrofluorometric experiments under different conditions (temperature, concentration, solvent viscosity). T-jump relaxation kinetics of the TO monomer-dimer conversion enabled the thermodynamic parameters of this process to be evaluated. The overall data collected provided information on the features of the "light-switch" by the fluorescent TO and the comparison between experimental and calculated photo-physical properties allowed us to explain and rationalize both shifts and quenching/enhancing effects on fluorescence due to solvation, dimerisation and intercalation in the DNA.     

Measurements of the tip leakage vortex structures and turbulence in the meridional plane of an axial water-jet pump

Particle image velocimetry (PIV) measurements at varying resolutions focus on the flow structures in the tip region of a water-jet pump rotor, including the tip-clearance flow and the rollup process of a tip leakage vortex (TLV). Unobstructed views of these regions are facilitated by matching the optical refractive index of the transparent pump with that of the fluid. High-magnification data reveal the flow non-uniformities and associated turbulence within the tip gap. Instantaneous data and statistics of spatial distributions and strength of vortices in the rotor passage reveal that the leakage flow emerges as a wall jet with a shear layer containing a train of vortex filaments extending from the tip of the blade. These vortices are entrained into the TLV, but do not have time to merge. TLV breakdown in the aft part of the blade passage further fragments these structures, increasing their number and reducing their size. Analogy is made between the circumferential development of the TLV in the blade passage and that of the starting jet vortex ring rollup. Subject to several assumptions, these flows display similar trends, including conditions for TLV separation from the shear layer feeding vorticity into it.     

On-line laser heating setup for ED-XAS at ID24: preliminary optical design and test results

Double-sided laser heating (LH) combined with synchrotron X-ray radiation for in situ studies in the diamond anvil cell (DAC) has been the most productive and widely used high-temperature–high pressure technique in the past two decades. In the framework of the UPBL11 project (upgrade of ID24 beamline of European Synchrotron Radiation Facility), we developed a new on-line LH system for DACs. The preliminary optical scheme of the system is presented and discussed. Varying the settings, we are able to shape and to size the beam on the surface of the sample in the DAC. First pilot applications to the Fe case are shown.     

On topologically distinct solutions of the Dirichlet problem for Yang-Mills connections

We prove that for generic Dirichlet boundary data there exist infinitely many topologically distinct solutions to the Dirichlet problem for -Yang-Mills equations over . These are absolute Yang-Mills minimizers in topologically distinct connected components of the space of connections considered. There is a special case for which only finitely many topologically distinct solutions can be found by our method. This corresponds to the simultaneous existence of self dual and anti-self dual solutions, for the given boundary data. If the boundary data is non-flat there exists always more than one solution. This paper generalizes to Yang-Mills fields an important result by Brezis and Coron, who show existence of more than one minimizing harmonic map for non-constant Dirichlet data in two dimensions. Received February 1, 1996 / Accepted March 15, 1996     

A characterization of hyperelliptic Jacobians

In this paper we will prove a criterion for hyperelliptic Jacobians. LetD be a translation invariant vector field on an indecompssable principally polarized abelian variety (i.p.p.a.v.) (X, Θ), letDΘ be the divisor of the sectionDΘ∈H ⁰ (Θ,O(Θ)|Θ). We have that (X, Θ) is the Jacobian of an hyperelliptic curve iff (Theorem 1) all the component ofDΘ are non reduced and the singular locus of Θ has dimension less thang-2. We will prove our theorem by showing that under the above geometrical condition it is possible to construct a Kodomcev-Petviashvili (K.P.) equation which is satisfied by the theta function corresponding to the principal polarization onX.     

A mixed algorithm for the calculation of rapidly varying fluid flows: The impulsively started circular cylinder

A mixed discrete Fourier transform-Finite difference algorithm is developed and used for the calculation of rapidly changing viscous fluid flows past a circular cylinder. The numerical approach has been designed to overcome certain difficulties arising for high Reynolds number simulations. The foremost advantage of the technique lies in its fast calculations of the convolution sums portraying the convective terms of the governing equations. Third-order spatial discretizations and fourth-order time marching are implemented. New schemes are proposed for the boundary conditions at the solid wall and at large distances. The techniques are tested on a case study with other schemes (summarized by Roache¹) in order to obtain an optimal choice. Definite indications on the stability and accuracy of boundary condition schemes are achieved. Support for the statement of dominant importance of boundary conditions is also given. A comparison of computational results with experimental data is presented for the case study of the flow past an impulsively started cylinder at Reynolds number 20. The time development of the symmetrical zone of recirculation, which is formed at an early stage of the flow, has been studied for 300 ≤ Re ≤ 9500 by means of the proposed algorithm. Computational results, comparisons with experimental data² and discussion of upper limits of validity of the procedure will be presented in a companion paper.     

Study of the missing-mass spectra in the reactions π−d → K+ + MM and K−d → π+ + MM at 1.4 GeV/c to search for strange dibaryon states

The reactions π^?d → K⁺ + MM and K^?d → π⁺ + MM have been studied at 1.4 GeV/c to search for strange dibaryon states with quantum numbers Q = ?1, and S = ?1. No structures are found which could indicate the production of such states and upper limits for the cross sections are established.