Sulfuration and reversion reactions of brominated poly(isobutylene‐co‐isoprene)

The sulfuration and reversion products of brominated poly(isobutylene‐co‐isoprene) (BIIR) were characterized through the use of a model compound, brominated 2,2,4,8,8‐pentamethyl‐4‐nonene (BPMN). The reaction of BPMN with S₈ produced bisallylic polysulfides of various ranks, yielding sulfur bromide intermediates that likely contributed to the rapid oxidation of allylic sulfides into thiophenes. Reductive cure reversion to pentamethylnonene was also observed in the latter stages of vulcanization. The reaction of 2,2′‐dithiobisbenzothiazole with BIIR and BPMN produced a stable adduct that reduced the concentration of allylic bromide available for vulcanization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1915–1926, 2003     

Comparison of carbon-silicon hyperconjugation at the 2- and 4-positions of the N-methylpyridinium cation

[structure: see text] N-Methyl-2-trialkylsilylmethylpyridinium cations 6a-c and 4-trialkylsilylmethylpyridinium cations 5a-c were prepared and investigated using (29)Si and (13)C NMR and single-crystal X-ray crystallography. Systematic differences in the (29)Si chemical shifts and (29)Si-(13)C one-bond coupling constants for these cations suggested that the Si-CH(2) bond interacts more strongly at the 2-position of the electron-deficient pyridinium ring than at the 4-position. This result is supported by the X-ray structures of the pyridinium cations 5b and 6b.     

An ultrasonic transducer array for velocity measurement in underwater vehicles

A correlation velocity log (CVL) is an ultrasonic navigation aid for marine applications, in which velocity is estimated using an acoustic transmitter and a receiver array. CVLs offer advantages over Doppler velocity logs (DVLs) in many autonomous underwater vehicle (AUV) applications, since they can achieve high accuracy at low velocities even during hover manoeuvres. DVLs require narrow beam widths, whilst ideal CVL transmitters have wide beam widths. This gives CVLs the potential to use lower frequencies thus permitting operation in deeper water, reducing power requirements for the same depth, or allowing the use of smaller transducers. Moving patterns in the wavefronts across a 2D receiver array are detected by calculating correlation coefficients between bottom reflections from consecutive transmitted pulses, across all combinations of receiver pairings. The position of the peak correlation value, on a surface representing receiver-pairing separations, is proportional to the vessel's displacement between pulses. A CVL aimed primarily for AUVs has been developed. Its acoustical and signal processing design has been optimised through sea trials and computer modelling of the sound field. This computer model is also used to predict how the distribution of the correlation coefficients varies with distance from the peak position. Current work seeks to increase the resolution of the peak estimate using surface fitting methods. Numerical simulations suggest that peak estimation methods significantly improve system precision when compared with simply identifying the position of the maximum correlation coefficient in the dataset. The peak position may be estimated by fitting a quadratic model to the measured data using least squares or maximum likelihood estimation. Alternatively, radial basis functions and Gaussian processes successfully predict the peak position despite variation between individual correlation datasets. This paper summarises the CVL's main acoustical features and signal processing techniques and includes results of sea trials using the device.     

Driving rate effects on crackling noise

Many systems respond to slowly changing external conditions with crackling noise, created by avalanches or pulses with a broad range of sizes. Examples range from Barkhausen noise (BN) in magnets to earthquakes. In this Letter, we discuss the effects of increasing driving rate Omega on the scaling behavior of the avalanche size and duration distributions as well as qualitative effects of Omega on the power spectra. We derive an exponent inequality as a criteria for the relevance of Omega. To illustrate these general results, we use recent experiments on BN as a successful example.     

Tunable single-frequency ultraviolet generation from a continuous-wave Ti : sapphire laser with an intracavity PPLN frequency doubler

We report a single-longitudinal-mode continuous-wave Ti:sapphire ring laser that is intracavity frequency doubled in periodically poled lithium niobate (PPLN). Using a multi-grating PPLN crystal, the second harmonic is tunable from 386 to 403 nm – close to the PPLN ultraviolet absorption edge – with a maximum generated power of 114 mW. The wavelength dependence of the critical operating temperature required to eliminate photorefractive effects in the PPLN crystal is determined. PACS 42.65.Ky; 42.70.Mp; 42.72.Bj     

Design of highly active iron-based catalysts for atom transfer radical polymerization: tridentate salicylaldiminato ligands affording near ideal Nernstian behavior

Iron(II) complexes bearing monoanionic tridentate salicyladiminato ligands are shown to be highly efficient catalysts for atom transfer radical polymerization (ATRP). Polymerization rates for styrene are among the highest reported for iron-mediated ATRP in nonpolar media, correlating well with E1/2 potentials and DeltaEp values for the complexes. The rigidity of the tridentate ligands, combined with ample space around the metal center to accommodate a halogen atom, we believe to be an important factor in the efficient ATRP behavior of these systems.     

Demonstration of a simple entangling optical gate and its use in bell-state analysis

We demonstrate a new architecture for an optical entangling gate that is significantly simpler than previous realizations, using partially polarizing beam splitters so that only a single optical mode-matching condition is required. We demonstrate operation of a controlled-z gate in both continuous-wave and pulsed regimes of operation, fully characterizing it in each case using quantum process tomography. We also demonstrate a fully resolving, nondeterministic optical Bell-state analyzer based on this controlled-z gate. This new architecture is ideally suited to guided optics implementations of optical gates.     

Search for the lepton-number-violating decay Xi(-)-->pmu(-)mu(-)

A sensitive search for the lepton-number-violating decay Xi(-)-->pmu(-)mu(-) has been performed using a sample of approximately 10(9) Xi(-) hyperons produced in 800 GeV/c p-Cu collisions. We obtain B(Xi(-)-->pmu(-)mu(-))<4.0x10(-8) at 90% confidence, improving on the best previous limit by 4 orders of magnitude.