Dependence of the kinetics of liquid-phase photocatalyzed reactions on oxygen concentration and light intensity

The initial kinetics of the oxidation of 4-chlorophenol, 4-CP, photocatalyzed by titania films and aqueous dispersions were studied as a function of oxygen partial pressure, P-O2, and incident light intensity, I. The reaction conditions were such that the kinetics were independent of [4-CP] but strongly dependent on PO2-a situation that allowed investigation of the less-often studied kinetics of oxygen reduction. The observed kinetics fit a pseudo-steady-state model in which the oxygen is Langmuir-adsorbed on the titania photocatalyst particles before being reduced by photogenerated electrons. The maximum rate of photocatalysis depends directly on I-beta, where, beta = 1 for films and 0.7 for dispersions of titania, indicating that the kinetics are dominated by the surface reactions of the photogenerated electrons and holes for the films and by direct recombination for the powder dispersions. Using the pseudo-first-order model, for both titania films and dispersions, the apparent Langmuir adsorption constant, K-LH, derived from a Langmuir-Hinshelwood analysis of the kinetics, appears to be largely independent of incident light intensity, unlike KLH for 4-CP Consequently, similar values are obtained for the Langmuir adsorption constant, K-ads, extracted from a pseudosteady-state analysis of the kinetics for oxygen on TiO2 dispersions and films in aqueous solution (i.e., ca. 0.0265 +/- 0.005 kPa(-1)), and for both films and dispersions, oxygen appears to be weakly adsorbed on TiO2 compared with 4-CP, at a rate that would take many minutes to reach equilibrium. The value of Kads for oxygen on titania particles dispersed in solution is ca. 4.7 times lower than that reported for the dark Langmuir adsorption isotherm; possible causes for this difference are discussed. (c) 2006 Elsevier Inc. All rights reserved.

Dependence of spatial coherence of 23.2-23.6-nm radiation on the geometry of a multielement germanium x-ray laser target

The spatial coherence of a nanosecond pulsed germanium collisionally excited x-ray laser is measured experimentally for three target configurations. The diagnostic is based on Young's slit interference fringes with a dispersing element to resolve the 23.2- and 23.6-nm spectral lines. Target configurations include a double-slab target, known as the injector, and geometries in which the injector image is image relayed to seed either an additional single-slab target or a second double-slab target. A special feature of this study is the observation of the change in the apparent source size with angle of refraction across the diverging laser beam. Source sizes derived with a Gaussian source model decrease from 44 mu m for the injector target by a variable factor of as much as 2, according to target configuration, for beams leaving the additional amplifiers after strong refraction in the plasma. (C) 1998 Optical Society of America [S0740-3224(98)00810-8].

Time dependence of the spatial coherence of the 23.6- and 23.2-nm radiation from the germanium soft-x-ray laser

The time dependence of the spatial coherence of the combined spectral lines at 23.2 and 23.6 nm from the Ge XXIII collisionally pumped soft-x-ray laser with a double-slab target is examined within a single nanosecond pulse by use of Young's interference fringes and a streak camera. High source intensity is linked with low spatial coherence and vice verse. Calculations of the source intensity, size, and position have also been made; these calculations refer to a single-slab source. Comparison between the observed and calculated intensities, and of the source sizes both calculated and derived from the Young's fringes by interpretation with a Gaussian model of source emission, show good agreement in general trends. (C) 1998 Optical Society of America [S0740-3224(98)01905-5].

The empirical metallicity dependence of the mass-loss rate of O- and early B-type stars

We present a comprehensive study of the observational dependence of the mass-loss rate in stationary stellar winds of hot massive stars on the metal content of their atmospheres. The metal content of stars in the Magellanic Clouds is discussed, and a critical assessment is given of state-of-the-art mass-loss determinations of OB stars in these two satellite systems and the Milky-Way. Assuming a power-law dependence of mass loss on metal content,. M. Z(m), and adopting a theoretical relation between the terminal flow velocity and metal content, v(infinity). Z(0.13) (Leitherer et al. 1992, ApJ, 401, 596), we find m = 0.83 +/- 0.16 for non-clumped outflows from an analysis of the wind momentum luminosity relation (WLR) for stars more luminous than 105.2 L circle dot. Within the errors, this result is in agreement with the prediction m = 0.69 +/- 0.10 by Vink et al. (2001, A& A, 369, 574). Absolute empirical values for the mass loss, based on Ha and ultraviolet (UV) wind lines, are found to be a factor of two higher than predictions in this high luminosity regime. If this difference is attributed to inhomogeneities in the wind, and this clumping does not impact the predictions, this would imply that luminous O and early-B stars have clumping factors in their Ha and UV line forming regions of about a factor of four. For lower luminosity stars, the winds are so weak that their strengths can generally no longer be derived from optical spectral lines (essentially Ha) and one must currently rely on the analysis of UV lines. We confirm that in this low-luminosity domain the observed Galactic WLR is found to be much steeper than expected from theory (although the specific sample is rather small), leading to a discrepancy between UV mass-loss rates and the predictions by a factor 100 at luminosities of L similar to 10(4.75) L circle dot, the origin of which is unknown. We emphasize that even if the current mass-loss rates of hot luminous stars would turn out to be overestimated as a result of wind clumping, but the degree of clumping would be rather independent of metallicity, the scalings derived in this study are expected to remain correct.

Polar distribution of ablated atomic material during the pulsed laser deposition of Cu in vacuum: Dependence on focused laser spot size and power density

Experiments have been carried out to investigate the polar distribution of atomic material ablated during the pulsed laser deposition of Cu in vacuum. Data were obtained as functions of focused laser spot size and power density. Thin films were deposited onto flat glass substrates and thickness profiles were transformed into polar atomic flux distributions of the form f(theta)=cos(n) theta. At constant focused laser power density on target, I=4.7+/-0.3X10(8) W/cm(2), polar distributions were found to broaden with a reduction in the focused laser spot size. The polar distribution exponent n varied from 15+/-2 to 7+/-1 for focused laser spot diameter variation from 2.5 to 1.4 mm, respectively, with the laser beam exhibiting a circular aspect on target. With the focused laser spot size held constant at phi=1.8 mm, polar distributions were observed to broaden with a reduction in the focused laser power density on target, with the associated polar distribution exponent n varying from 13+/-1.5 to 8+/-1 for focused laser power density variation from 8.3+/-0.3X10(8) to 2.2+/-0.1X10(8) W/cm(2) respectively. Data were compared with an analytical model available within the literature, which correctly predicts broadening of the polar distribution with a reduction in focused laser spot size and with a reduction in focused laser power density, although the experimentally observed magnitude was greater than that predicted in both cases. (C) 1996 American Institute of Physics.

Dependence of laser accelerated protons on laser energy following the interaction of defocused, intense laser pulses with ultra-thin targets

The scaling of the flux and maximum energy of laser-driven sheath-accelerated protons has been investigated as a function of laser pulse energy in the range of 15-380 mJ at intensities of 10(16)-10(18) W/cm(2). The pulse duration and target thickness were fixed at 40 fs and 25 nm, respectively, while the laser focal spot size and drive energy were varied. Our results indicate that while the maximum proton energy is dependent on the laser energy and laser spot diameter, the proton flux is primarily related to the laser pulse energy under the conditions studied here. Our measurements show that increasing the laser energy by an order of magnitude results in a more than 500-fold increase in the observed proton flux. Whereas, an order of magnitude increase in the laser intensity generated by decreasing the laser focal spot size, at constant laser energy, gives rise to less than a tenfold increase in observed proton flux.

A multiple-radical model for radiation action on DNA and the dependence of OER on LET

We have a developed a multiple-radical model of the chemical modification reactions involving oxygen and thiols relevant to the interactions of ionizing radiations with DNA. The treatment is based on the Alper and Howard-Flanders equation but considers the case where more than one radical may be involved in the production of lesions in DNA. This model makes several predictions regarding the induction of double strand breaks in DNA by ionizing radiation and the role of sensitizers such as oxygen and protectors such as thiols which act at the chemical phase of radiation action via the involvement of free radicals. The model predicts a decreasing OER with increasing LET on the basis that as radical multiplicity increases so will the probability that, even under hypoxia, damage will be fixed and lead to lesion production. The model can be considered to provide an alternative hypothesis to those of 'interacting radicals' or of 'oxygen-in-the-track'.