Electrophilic aromatic substitution by the fluorofullerene C60F18

The FeCl3-catalysed arylation of C60F18 gives tri-substituted compounds C60F15Ar3, where Ar=phenyl, 4-tolyl, 4-methoxyphenyl, 4-phenoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-biphylenyl and 2-fluorenyl, together with some bis- and mono-substituted product. Bis-substitution was achieved with biphenylene and fluoranthene, and mono-substitution with biphenylene (2-position), pyrene (1-position), and naphthalene (1- and 2-positions); the tris-phenyl and tris-biphenylene derivatives are fluorescent. The 2-naphthyl substituent freely rotates at 328 K, whereas rotation of the 1-naphthyl substituent is prevented by interaction of the peri-hydrogen atom with fluorine. The 1-naphthyl derivative eliminates a molecule of HF during EI mass spectrometry, whilst the 2-naphthyl derivative eliminates HF and all fluorenes to give a naphthaleno[60]fullerene. The reaction rate is relatively unaffected by electron supply in the aryl rings, but no product was obtained with benzotrifluoride which defines the lower reactivity limit. The low discrimination between aromatics makes it possible to isolate derivatives having different aryl groups attached to the cage. Reactions occur mainly when the reagent solutions (or solutions in 1,2-dichlorobenzene) are evaporated to dryness. In most FeCl3-catalysed reactions, unreacted C60F18 was recovered, more if the less effective SnCl4 was used as a catalyst; use of AlCl3 resulted in polyarylation and degradation of the C60F18. The structure of C60F17(1-biphenylyl) was confirmed by single-crystal X-ray analysis. Reaction of C60F18 with perylene/FeCl3/o-dichlorobenzene gave red fluorescent "tagliatelli"-like threads (up to 1 cm long) of self-assembled pi-stacked tetrachloroperylene arising from chlorination by FeCl3.     

A four-electron O(2)-electroreduction biocatalyst superior to platinum and a biofuel cell operating at 0.88 V

O2 was electroreduced to water, at a true-surface-area-based current density of 0.5 mA cm-2, at 37 degrees C and at pH 5 on a "wired" laccase bioelectrocatalyst-coated carbon fiber cathode. The polarization (potential vs the reversible potential of the O2 /H2O half-cell in the same electrolyte) of the cathode was only -0.07 V, approximately one-fifth of the -0.37 V polarization of a smooth platinum fiber cathode, operating in its optimal electrolyte, 0.5 M H2SO4. The bioelectrocatalyst was formed by "wiring" laccase to carbon through an electron conducting redox hydrogel, its redox functions tethered through long and flexible spacers to its cross-linked and hydrated polymer. Incorporation of the tethers increased the apparent electron diffusion coefficient 100-fold to (7.6 +/- 0.3) x 10-7 cm 2 s-1. A miniature single-compartment glucose-O2 biofuel cell made with the novel cathode operated optimally at 0.88 V, the highest operating voltage for a compartmentless miniature fuel cell.     

Automated high-capacity sorption probe for extraction of organic compounds in aqueous samples followed by gas chromatographic analysis

An automated high-capacity sorption device for GC analysis of ultra trace components has been developed. The scope of the presented technique was to combine the simplicity of solid-phase microextraction (SPME) with the high extraction efficiency of the stir bar sorptive extraction technology. Sorptive extractions of water samples were performed using polydimethylsiloxane (PDMS) rubber tubing (120 microl) mounted onto a glass rod. The sampling procedure was carried out by a robotic autoinjector. Since the setup is fully automated, unattended and precise time-controlled extraction of samples is possible and makes quantitation with non-equilibrium extractions feasible. The sorption probes are easy to exchange, which facilitates off-line/in-field sampling. The system was evaluated with a test mixture of 44 environmentally hazardous compounds. Detection limits were found to be in the sub-ppt region. The performance of the system was demonstrated with the analysis of polycyclic aromatic hydrocarbons in urban snow.     

Global simulation for laser-driven MeV electrons in fast ignition

A comprehensive examination of the interaction of a picosecond-long ignition pulse on high-density (40 times critical density) pellets using a two-dimensional particle-in-cell model is described. The global geometry consists of a 50 mum diameter pellet surrounded by a corona which is isolated by a vacuum region from the boundary. For cone-attached targets, as much as 67% of the incident laser energy is absorbed with 12% sent forward as fast electrons in a 23 degrees cone. The current filaments are driven by the Weibel instability of the forward-going fast electron flux and its return current with the ions playing an important role of neutralizing the space charge. No global current filament coalescence has been observed. The electron distribution function obeys a power law, which begins at E approximately 0.2 MeV and falls off as E-(2-3).     

Engineering mixed states in a degenerate four-state system

A method is proposed for preparing any pure and wide class of mixed quantum states in the decoherence-free ground-state subspace of a degenerate multilevel lambda system. The scheme is a combination of optical pumping and a series of coherent excitation processes, and for a given pulse sequence the same final state is obtained regardless of the initial state of the system. The method is robust with respect to the fluctuation of the pulse areas, as in adiabatic methods; however, the field amplitude can be adjusted in a larger range.     

Optimal dispersion relations for enhanced electromagnetic power deposition in dissipative slabs

Broadband analysis of a prototype model associated with electromagnetic waves absorption in a lossy dielectric slab renders a closed-form theoretical prediction of an infinite number of optimal absorption paths in the complex refractive index domain. While for thin slabs (in terms of incident wavelength range) each path corresponds to a lossy Fabry-Perot-type resonance modes of order m=0,1,2,... and provides at least 50% absorption of the incident wave power even for ultrathin slabs, for optimal thick slabs, the fraction of absorbed power, asymptotically estimated via Lambert W function, increases up to 100% for consecutive continuation of the m=1 normal mode only.     

Uniqueness of travelling waves for nonlocal monostable equations

We consider a nonlocal analogue of the Fisher-KPP equation

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and its discrete counterpart , , and show that travelling wave solutions of these equations that are bounded between and are unique up to translation. Our proof requires finding exact a priori asymptotics of a travelling wave. This we accomplish with the help of Ikehara's Theorem (which is a Tauberian theorem for Laplace transforms).

     

Improving motion estimation by accounting for local image distortion

Cardiac elastography is a useful diagnostic technique for detection of heart function abnormalities, based on analysis of echocardiograms. The analysis of the regional heart motion allows assessing the extent of myocardial ischemia and infarction. In this paper, a new two-stage algorithm for cardiac motion estimation is proposed, where the data is taken from a sequence of 2D echocardiograms. The method combines the advantages of block-matching and optical flow techniques. The first stage employs a standard block-matching algorithm (sum of absolute differences) to provide a displacement estimate with accuracy of up to one pixel. At the second stage, this estimate is corrected by estimating the parameters of a local image transform within a test window. The parameters of the image transform are estimated in the least-square sense. In order to account for typical heart motions, like contraction/expansion, translation and rotation, a local affine model is assumed within the test window. The accuracy of the new algorithm is evaluated using a sequence of 500 grayscale B-mode images, which are generated as distorted, but known copies of an original ROI, taken from a real echocardiogram. The accuracy of the motion estimation is expressed in terms of errors: maximum absolute error, root-mean-square error, average error and standard deviation. The errors of the proposed algorithm are compared with these of the known block-matching technique with cross-correlation and interpolation in the sub-pixel space. Statistical analysis of the errors shows that the proposed algorithm provides more accurate estimates of the heart motion than the cross-correlation technique with interpolation in the sub-pixel space.     

Observation of collective-emission-induced cooling of atoms in an optical cavity

We report the observation of collective-emission-induced, velocity-dependent light forces. One-third of a falling sample containing 3 x 10(6) cesium atoms illuminated by a horizontal standing wave is stopped by cooperatively emitting light into a vertically oriented, confocal resonator. We observe decelerations up to 1500 m/s(2) and cooling to temperatures as low as 7 microK, well below the free-space Doppler limit. The measured forces substantially exceed those predicted for a single two-level atom.     

Resummed photon spectrum in radiative upsilon decays

We present a theoretical prediction for the photon spectrum in radiative upsilon decay including the effects of resumming the end point region, E(gamma)-->M(upsilon)/2. Our approach is based on nonrelativistic QCD (NRQCD) and the soft-collinear effective theory. We find that our results give much better agreement with data than the leading order NRQCD prediction.