Thermolysis and Chemiluminescence of Monocyclic 1,2,4-Trioxan-5-ones

The 3,6-substituted 1,2,4-trioxan-5-ones 11 – 14 , on heating to 170–200°, underwent unimolecular thermolysis to generate electronically excited singlet ketones with an efficiency of ca. 0.2%. The chemiluminescence quantum yields (?oS_CL) depended on the nature of the 6-substitutents and increased linearly with temperature. The Arrhenius activation energies were obtained by measuring the rate of decay of luminescence and determined as 22.9, 30.4, 35.6, and 34.2 kcal/mol for 11 – 14 , respectively. Step analysis of the chemiluminescence of 14 afforded an average activation energy of 44.3 kcal/mol. This latter result is explicable in terms of two decomposition paths, higher and lower in energy, leading to excited and ‘dark’ products, respectively. The thermolysis of trioxanones 12 – 14 lacking a H-atom at the 6-position is interpreted as involving successive rupture of the peroxide bond, excision of ketone at the 3-substituted end, and loss of CO₂, to finally produce ketone originating from the 6-position (see Scheme 4).     

A NEW FINITE ELEMENT APPROXIMATION OF A STATE-CONSTRAINED OPTIMAL CONTROL PROBLEM

In this paper, we study numerical methods for an optimal control problem with pointwise state constraints. The traditional approaches often need to deal with the deltasingularity in the dual equation, which causes many difficulties in its theoretical analysis and numerical approximation. In our new approach we reformulate the state-constrained optimal control as a constrained minimization problems only involving the state, whose optimality condition is characterized by a fourth order elliptic variational inequality. Then direct numerical algorithms （nonconforming finite element approximation） are proposed for the inequality, and error estimates of the finite element approximation are derived. Numerical experiments illustrate the effectiveness of the new approach.     

Source motion detection, estimation, and compensation for underwater acoustics inversion by wideband ambiguity lag-Doppler filtering

Acoustic channel properties in a shallow water environment with moving source and receiver are difficult to investigate. In fact, when the source-receiver relative position changes, the underwater environment causes multipath and Doppler scale changes on the transmitted signal over low-to-medium frequencies (300 Hz-20 kHz). This is the result of a combination of multiple paths propagation, source and receiver motions, as well as sea surface motion or water column fast changes. This paper investigates underwater acoustic channel properties in a shallow water (up to 150 m depth) and moving source-receiver conditions using extracted time-scale features of the propagation channel model for low-to-medium frequencies. An average impulse response of one transmission is estimated using the physical characteristics of propagation and the wideband ambiguity plane. Since a different Doppler scale should be considered for each propagating signal, a time-warping filtering method is proposed to estimate the channel time delay and Doppler scale attributes for each propagating path. The proposed method enables the estimation of motion-compensated impulse responses, where different Doppler scaling factors are considered for the different time delays. It was validated for channel profiles using real data from the BASE'07 experiment conducted by the North Atlantic Treaty Organization Undersea Research Center in the shallow water environment of the Malta Plateau, South Sicily. This paper provides a contribution to many field applications including passive ocean tomography with unknown natural sources position and movement. Another example is active ocean tomography where sources motion enables to rapidly cover one operational area for rapid environmental assessment and hydrophones may be drifting in order to avoid additional flow noise.     

Influencing the angular emission of a single molecule

We present the first experimental proof for the influence of a nearby nanosized metal object on the angular photon emission by a single molecule. Using a novel angular sensitive detection scheme, we directly quantify the redirection of angular emission for different molecular dipole orientations as an object is scanned laterally over the molecule at different heights. An excellent agreement between experiments and 2D-numerical simulations is found for molecules oriented perpendicular to the sample, whereas, for parallel orientations, the observed behavior contradicts the calculated behavior.     

Local observations of phase singularities in optical fields in waveguide structures

A linear copolymer made of two reciprocally attracting N-monomer blocks collapses to a compact phase through a novel transition, whose exponents are determined with extensive Monte Carlo simulations in two and three dimensions. In the former case, an identification with the statistical geometry of suitable percolation paths allows one to predict that the number of contacts between the blocks grows like N9/16. In the compact phase the blocks are mixed and, in two dimensions, also zipped, in such a way to form a spiral, double chain structure.     

Total charge-changing cross sections for neutron-deficient isotopes from58Ni fragmentation

At the projectile-fragment separator FRS of GSI, relativistic secondary beams of about 520 MeV/nucleon were produced by fragmentation of a primary beam of⁵⁸Ni at 650 MeV/nucleon in a beryllium target. By means of aΔE—Bρ—TOF measurement, the fragments have been identified and their charge-changing probabilities in targets of CH₂, C, Al, and Pb have been determined. We describe the results for the total charge-changing cross sections in this first paper, whereas a second article deals with the partial charge-changing cross sections. At the drip line, the measured charge-changing cross sections exhaust close to 100% of the total interaction cross sections as calculated with semiempirical models. The measurements at the proton drip line with low-Z targets indicate that only a very small increase of the cross sections may be observed, whereas the measurements with a lead target show that no significant increase of the total charge-changing cross sections is present which would be a hint for low-lying dipole strength. Our experimental data are compared to Glauber-type calculations.     

Partial charge-changing cross sections for neutron-deficient isotopes from58Ni fragmentation

At the projectile-fragment separator FRS of GSI, relativistic secondary beams of about 520 MeV/nucleon were produced by fragmentation of a primary beam of⁵⁸Ni at 650 MeV/nucleon in a beryllium target. By means of aE—B—TOF measurement, the fragments were identified and their charge-changing probabilities in targets of (CH₂) _n , C, Al, and Pb placed at the exit of the FRS were determined. Whereas a first article dealt with the total charge-changing cross sections, we describe in this second article the element distributions of these secondary fragments, which are found to depend strongly on the isospin of the secondary projectile as well as on the target material. In the case of the lead target, the influence of the electromagnetic dissociation is clearly visible in the one-proton and two-proton removal channels. The preference for the formation of even-Z fragments is much more pronounced for exotic secondary projectiles than for projectiles close to stability. Calculations with a geometrical abrasion-ablation model allow to understand the global features of the experimental data. However, far from stability, the discrepancies between calculations and experimental data increase.On leave of absence from Institute of Experimental Physics, University of Warsaw, PL-00-681 Warszawa, Hoa 69, Poland