Comments on the Meehl-Waller (2002) procedure for appraisal of path analysis models.

P. E. Meehl and N. G. Waller (see record 2002-18342-001) proposed an innovative method for assessing path analysis models wherein they subjected a given model, along with a set of alternatives, to risky tests using selected elements of a sample correlation matrix. Although the authors find much common ground with the perspective underlying the Meehl-Waller approach, they suggest that there are aspects of the proposed procedure that require close examination and further development. These include the selection of only one subset of correlations to estimate parameters when multiple solutions are generally available, the fact that the risky tests may test only a subset of parameters rather than the full model of interest, and the potential for different results to be obtained from analysis of equivalent models. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Assessing the contribution of free hydroxyl radical in organic matter-sensitized photohydroxylation reactions

Photochemical formation of reactive oxygen species from dissolved organic matter (DOM) is incompletely understood, especially in the case of hydroxyl radical (?OH) production. Many studies have used various probes to detect photochemically produced ?OH from DOM, but the fundamental reactions of these probes are not necessarily specific for free ?OH and may also detect lower-energy hydroxylation agents. In this study, two tests were applied that have previously been used as a diagnostic for the presence of free ?OH: methane quenching of ?OH and hydroxybenzoic acid (hBZA) product yields. Upon application of these two tests to a set of five DOM isolates, it was found that methane quenching and the hBZA ratio results were not necessarily consistent. Overall, the results provide compelling evidence that all isolates studied photochemically produce free ?OH. The hydroxylating acitivity of Elliot Soil Humic Acid and Pony Lake Fulvic Acid, however, also had a significant contribution from a photochemically generated hydroxylating agent that is lower in energy than free ?OH. Catalase quenching experiments were conducted to assess whether hydrogen peroxide was the immediate precursor to hydroxyl in these systems. In all cases, catalase addition slowed photohydroxylation of terephthalate, but the contribution of hydrogen peroxide photolysis was determined to be less than 50%.     

Applications of analytical electron microscopy to guide the design of boron carbide

Compositional analysis of boron carbide on nanometer length scales to examine or interpret atomic mechanisms, for example, solid-state amorphization or grain-boundary segregation, is challenging. This work reviews advancements in high-resolution microanalysis to characterize multiple generations of boron carbide. First, ζ-factor microanalysis will be introduced as a powerful (scanning) transmission electron microscopy ((S)TEM) analytical framework to accurately characterize boron carbide. Three case studies involving the application of ζ-factor microanalysis will then be presented: (1) accurate stoichiometry determination of B-doped boron carbide using ζ-factor microanalysis and electron energy loss spectroscopy, (2) normalized quantification of silicon grain-boundary segregation in Si-doped boron carbide, and (3) calibration of a scanning electron microscope X-ray energy-dispersive spectroscopy (XEDS) system to measure compositional homogeneity differences of B/Si-doped arc-melted boron carbides in the as-melted and annealed conditions. Overall, the improvement and application of advanced analytical tools have helped better understand processing–microstructure–property relationships and successfully manufacture high-performance ceramics.     

Synthesis and characterization of TiO2 nanotube/hydroquinone hybrid structure

It is shown that 1,4-benzenediol (hydroquinone) and TiO2 nanotubes can form a hybrid structure that is stable in aqueous environment. The incorporation of hydroquinone restores the local structure of nanotubes to anatase-like as evidenced by Raman spectroscopy. Subtle overall structural changes take place upon annealing of the hybrid structure contributing to its stability. The hybrid system shows a broad optical absorption peak extending significantly beyond 700 nm with potential applications in photocatalysis and photoelectrochemistry.     

Efficient and monolithic polarization conversion system based on a polarization grating

We introduce a new polarization conversion system (PCS) based on a liquid-crystal polarization grating (PG) and louvered wave plate. A simple arrangement of these elements laminated between two microlens arrays results in a compact and monolithic element, with the ability to nearly completely convert unpolarized input into linearly polarized output across most of the visible bandwidth. In our first prototypes, this PG-PCS approach manifests nearly 90% conversion efficiency of unpolarized to polarized for ±11° input light divergence, leading to an energy efficient picoprojector that presents high efficacy (12 lm/W) with good color uniformity.     

Loneliness impairs daytime functioning but not sleep duration.

Objective: To assess the prospective association between daily feelings of loneliness and subsequent feelings of daytime dysfunction indicative of poor sleep quality. Design: Three consecutive end-of-day diaries were completed by a population-based sample of 215 adults (mean age = 57.5 years, SD = 4.4). Diary questions probed sleep duration, daytime dysfunction (i.e., fatigue, low energy, sleepiness), loneliness, physical symptoms, and depressed affect experienced that day. Chronic health condition data and body mass index were also obtained. Autoregressive cross-lagged panel models were used to examine the magnitude of reciprocal prospective associations between loneliness and daytime dysfunction. Main Outcome Measures: Unstandardized path coefficients adjusted for race/ethnicity, sleep duration, marital status, household income, chronic health conditions, and health symptom severity. Results: Daily variations in loneliness predicted subsequent feelings of daytime dysfunction (B = 0.16, p     

Hydrodefluorination and Hydrogenation of Fluorobenzene under Mild Aqueous Conditions

Fluorinated organic compounds are increasingly used in many applications, and their release to the environment is expected. It is therefore important to find suitable methods for degradation of fluorinated compounds under environmentally relevant conditions. In this study, a simple heterogeneous rhodium-based catalytic system (Rh/Al(2)O(3) and H(2)) for hydrodefluorination and hydrogenation of fluorobenzene under mild aqueous conditions (1 atm of H(2), ambient temperature) was developed and the underlying reaction mechanism was investigated. Fluorobenzene degraded rapidly (t(1/2) ≈ 0.2 h) to form cyclohexane and fluoride (F(-)) as the stable end products, with benzene and cyclohexene observed as intermediates. Cyclohexadiene intermediates were not observed but were expected to form during the hydrogenation of benzene. Three postulated but unobserved fluorinated intermediates were subjected to the catalytic reaction conditions, and it was concluded that they most likely do not form during the fluorobenzene degradation reaction. Isotope labeling experiments showed that the unsaturated intermediates undergo rapid and reversible hydrogenation/dehydrogenation under the reaction conditions and also that fully saturated compounds are unreactive in the catalytic system. Both molecular hydrogen and water were sources of hydrogen in the final cyclohexane product. Kinetic fitting indicated that sorption/desorption of fluorobenzene onto the catalyst surface plays an important role in the mechanism.     

Hydroxyl radical formation upon oxidation of reduced humic acids by oxygen in the dark

Humic acids (HAs) accept and donate electrons in many biogeochemical redox reactions at oxic/anoxic interfaces. The products of oxidation of reduced HAs by O(2) are unknown but are expected to yield reactive oxygen species, potentially including hydroxyl radical (·OH). To quantify the formation of ·OH upon oxidation of reduced HAs by O(2), three HAs were reduced electrochemically to well-defined redox states and were subsequently oxidized by O(2) in the presence of the ·OH probe terephthalate. The formation of ·OH upon oxidation increased with increasing extent of HA reduction. The yield of ·OH ranged from 42 to 160 mmol per mole of electrons donated by the reduced HA. The intermediacy of hydrogen peroxide (H(2)O(2)) in the formation of ·OH was supported by enhancement of ·OH formation upon addition of exogenous H(2)O(2) sources and by the suppression of ·OH formation upon addition of catalase as a quencher of endogenous H(2)O(2). The formation of ·OH in the dark during oxidation of reduced HA represents a previously unknown source of ·OH formation at oxic/anoxic interfaces and may affect the biogeochemical and pollutant redox dynamics at these interfaces.     

Spatial and temporal distribution of singlet oxygen in Lake Superior

A multiyear field study was undertaken on Lake Superior to investigate singlet oxygen ((1)O(2)) photoproduction. Specifically, trends within the lake were examined, along with an assessment of whether correlations existed between chromophoric dissolved organic matter (CDOM) characteristics and (1)O(2) production rates and quantum yields. Quantum yield values were determined and used to estimate noontime surface (1)O(2) steady-state concentrations ([(1)O(2)](ss)). Samples were subdivided into three categories based on their absorbance properties (a300): riverine, river-impacted, or open lake sites. Using calculated surface [(1)O(2)](ss), photochemical half-lives under continuous summer sunlight were calculated for cimetidine, a pharmaceutical whose reaction with (1)O(2) has been established, to be on the order of hours, days, and a week for the riverine, river-impacted, and open lake waters, respectively. Of the CDOM properties investigated, it was found that dissolved organic carbon (DOC) and a300 were the best parameters for predicting production rates of [(1)O(2)](ss). For example, given the correlations found, one could predict [(1)O(2)](ss) within a factor of 4 using a300 alone. Changes in the quantum efficiency of (1)O(2) production upon dilution of river water samples with lake water samples demonstrated that the CDOM found in the open lake is not simply diluted riverine organic matter. The open lake pool was characterized by low absorption coefficient, low fluorescence, and low DOC, but more highly efficient (1)O(2) production and predominates the Lake Superior system spatially. This study establishes that parameters that reflect the quantity of CDOM (e.g., a300 and DOC) correlate with (1)O(2) production rates, while parameters that characterize the absorbance spectrum (e.g., spectral slope coefficient and E2:E3) correlate with (1)O(2) production quantum yields.