Spontaneous Chelation-Driven Reduction of the Neptunyl Cation in Aqueous Solution

Octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) siderophore analogues are known to be efficacious chelators of the actinide cations, and these ligands are also capable of facilitating both activation and reduction of actinyl species. Utilizing X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, as well as cyclic voltammetry measurements, herein, we elucidate chelation-based mechanisms for driving reactivity and initiating redox processes in a family of neptunyl–HOPO and CAM complexes. Based on the selected chelator, the ability to control the oxidation state of neptunium and the speed of reduction and concurrent oxo group activation was demonstrated. Most notably, reduction kinetics for the Np^VO₂^+//Np^IV redox couple upon chelation by the ligands 3,4,3-LI(1,2-HOPO) and 3,4,3-LI(CAM)₂(1,2-HOPO)₂ was observed to be faster than ever reported, and in fact quicker than we could measure using either X-ray absorption spectroscopy or electrochemical techniques.     

420-MHz Cr:forsterite femtosecond ring laser and continuum generation in the 1-2-micrometre range

We demonstrate a chromium-doped forsterite femtosecond ring laser that generates 30-fs pulses at a 420-MHz repetition rate with nearly 500 mW of average power. The compact solid-state design and broad spectral output make this laser attractive for telecommunications applications in the 1.3-1.5-micrometre region. Additional spectral broadening of the laser output in highly nonlinear optical fiber leads to octave-spanning spectra ranging from 1.06 to 2.17 micrometre. The octave is reached at a level of 18 dB below the peak. The underlying optical frequency comb can be linked to existing optical frequency standards.     

Noise amplification during supercontinuum generation in microstructure fiber

Supercontinua generated by femtosecond pulses launched in microstructure fiber can exhibit significant low-frequency (<1-MHz) amplitude noise on the output pulse train. We show that this low-frequency noise is an amplified version of the amplitude noise that is already present on the input laser pulse train. Through both experimental measurements and numerical simulations, we quantify the noise amplification factor and its dependence on the supercontinuum wavelength and on the energy and duration of the input pulse. Interestingly, the dependence differs significantly from that of the broadband white-noise component, which arises from amplification of the input laser shot noise.     

Density dependence of the transition temperature in a homogeneous bose-einstein condensate

Transition temperature data obtained as a function of particle density in the 4He-Vycor system are compared with recent theoretical calculations for 3D Bose-condensed systems. In the low density dilute Bose gas regime we find, in agreement with theory, a positive shift in the transition temperature of the form DeltaT/T0 = gamma(na(3))(1/3). At higher densities a maximum is found in the ratio of T(c)/T0 for a value of the interaction parameter, na(3), that is in agreement with path-integral Monte Carlo calculations.     

Experiments with longitudinally polarized electrons in a storage ring using a siberian snake

We report on first measurements with polarized electrons stored in a medium-energy ring and with a polarized internal target. Polarized electrons were injected at 442 MeV (653 MeV), and a partial (full) Siberian snake was employed to preserve the polarization. Longitudinal polarization at the interaction point and polarization lifetime of the stored electrons were determined with laser backscattering. Spin observables were measured for electrodisintegration of polarized 3He, with simultaneous detection of scattered electrons, protons, neutrons, deuterons, and 3He nuclei, over a large phase space.     

Gas-mediated impact dynamics in fine-grained granular materials

Noncohesive granular media exhibit complex responses to sudden impact that often differ from those of ordinary solids and liquids. We investigate how this response is mediated by the presence of interstitial gas between the grains. Using high-speed x-ray radiography we track the motion of a steel sphere through the interior of a bed of fine, loose granular material. We find a crossover from nearly incompressible, fluidlike behavior at atmospheric pressure to a highly compressible, dissipative response once most of the gas is evacuated. We discuss these results in light of recent proposals for the drag force in granular media.     

Bis(permethylpentalene)cerium--another ambiguity in lanthanide oxidation state

Ce(eta(8)-C(8)Me(6))(2) exists in a valency close to Ce(iii) with some Ce(iv) and provides an example of the Kondo effect in a discrete molecule.