The effect of Pt oxidation state and concentration on the photocatalytic removal of aqueous ammonia with Pt-modified titania

Platinum-modified titanium (IV) oxide (Pt-TiO₂) was used to photocatalytically oxidize aqueous ammonia selectively to nitrogen gas. The photocatalyst was solvent deposited on acrylic (PMMA) supports for use in simple distributive reactors. Pt was photodeposited on the titania surface within each reactor with concentrations ranging from 0.4% (w/w) to 5.1% (w/w) Pt. The oxidation state of the deposited Pt was subsequently modified using reduced phosphotungstic acid. Time-dependent kinetic studies were used to demonstrate the effect of oxidation state on the photocatalytic activity of the Pt-TiO₂. It was determined that treatment with reduced phosphotungstic acid enhanced the reaction rate and selectivity to nitrogen gas of the Pt-TiO₂ photocatalysts. Most significantly, treatment of Pt-TiO₂ with reduced phosphotungstic acid shifts the optimum Pt concentration to higher Pt loadings. The reactor containing 3.2% (w/w) post-treated Pt demonstrated the most favorable combination of NH₃ degradation rate and selectivity to N₂, resulting in the removal of 28.34% total nitrogen from 1.7 L of a 45.5 ppm NH₃-N solution within 72 h.     

XAS and microscopy studies of the uptake and bio-transformation of copper in Larrea tridentata (creosote bush)

Herein we present work directed toward understanding the mechanisms employed by Larrea tridentata (Creosote bush) to uptake and simultaneously defend against the presence of excess copper. The location and nature of copper in the plant have been studied on several length scales: greater than 10 μm (scanning electron microscopy), less than 10 μm (transmission electron microscopy) and atomic level structure and speciation (EXAFS and XANES). Two interesting results are apparent: creosote takes up or adsorbs copper from the soil in the Cu(II) oxidation state and transports it to the leaves where copper is found as Cu(I) and Cu(II). The transport agent appears to be a Cu phytochelatin. Additionally, creosote may be immobilizing and excreting copper via at least two additional mechanisms: storage of metals in vacuoles and excretion of copper into the sticky resinous substance found on the leaf surface. Creosote may also accumulate wind-blown particulates that can easily adhere to the resinous sticky surface of the plant. If, however, the particulates are <10 μm they may enter the leaf by respiration through the plant ‘stomata’ that have openings between 5 μm and 10 μm. As such, creosote may be a natural bio-indicator for airborne particulates that are <10 μm.     

Statistical characterization of meso-scale uniaxial compressive strength in brittle materials with randomly occurring flaws

Increasingly fine spatial resolution in numerical models of brittle materials promises to improve prediction and characterization of dynamic failure in these materials. However, as the resolution of these numerical models begins to approach the material micro-scale, the associated discretization requires a definitive connection to the microstructure. In many cases a numerical model (e.g., a finite element mesh) that explicitly resolves each flaw within the material is not feasible for macro-scale analyses. As an alternative, each element can be treated as a meso-scale continuum with constitutive properties that reflect the characteristics of the underlying microstructure. Small scale elements will exhibit random variations in the constitutive properties as a result of the random variations in the number and types of flaws and the flaw sizes contained within each element. The present paper proposes a technique for assigning probability distributions to these element properties, which can be thought of as the meso-scale constitutive properties. In particular, the strain-rate dependent compressive uniaxial strength of a ceramic is modeled using a two-dimensional analytical model developed by Paliwal and Ramesh (2008). The effect on the probability distribution of meso-scale (or element-level) strength from flaw density, flaw size distribution, flaw clustering, and strain rate are studied. Higher strain rates, more flaw clustering, and decreasing element size all contribute to greater scatter in uniaxial compressive strength. Variations in flaw size increase the scatter in the strength more for low strain rate loadings and less clustered microstructures. The results provide interesting comparisons to the classical assumption of a two-parameter Weibull-distributed strength, showing that a three-parameter Weibull distribution and even a lognormal distribution fit better with the simulated strength data.     

Auditory discontinuities interact with categorization: implications for speech perception

Behavioral experiments with infants, adults, and nonhuman animals converge with neurophysiological findings to suggest that there is a discontinuity in auditory processing of stimulus components differing in onset time by about 20 ms. This discontinuity has been implicated as a basis for boundaries between speech categories distinguished by voice onset time (VOT). Here, it is investigated how this discontinuity interacts with the learning of novel perceptual categories. Adult listeners were trained to categorize nonspeech stimuli that mimicked certain temporal properties of VOT stimuli. One group of listeners learned categories with a boundary coincident with the perceptual discontinuity. Another group learned categories defined such that the perceptual discontinuity fell within a category. Listeners in the latter group required significantly more experience to reach criterion categorization performance. Evidence of interactions between the perceptual discontinuity and the learned categories extended to generalization tests as well. It has been hypothesized that languages make use of perceptual discontinuities to promote distinctiveness among sounds within a language inventory. The present data suggest that discontinuities interact with category learning. As such, "learnability" may play a predictive role in selection of language sound inventories.     

Incidental categorization of spectrally complex non-invariant auditory stimuli in a computer game task

This study examined perceptual learning of spectrally complex nonspeech auditory categories in an interactive multi-modal training paradigm. Participants played a computer game in which they navigated through a three-dimensional space while responding to animated characters encountered along the way. Characters' appearances in the game correlated with distinctive sound category distributions, exemplars of which repeated each time the characters were encountered. As the game progressed, the speed and difficulty of required tasks increased and characters became harder to identify visually, so quick identification of approaching characters by sound patterns was, although never required or encouraged, of gradually increasing benefit. After 30 min of play, participants performed a categorization task, matching sounds to characters. Despite not being informed of audio-visual correlations, participants exhibited reliable learning of these patterns at posttest. Categorization accuracy was related to several measures of game performance and category learning was sensitive to category distribution differences modeling acoustic structures of speech categories. Category knowledge resulting from the game was qualitatively different from that gained from an explicit unsupervised categorization task involving the same stimuli. Results are discussed with respect to information sources and mechanisms involved in acquiring complex, context-dependent auditory categories, including phonetic categories, and to multi-modal statistical learning.     

Possible observation of phase separation near a quantum phase transition in doubly connected ultrathin superconducting cylinders of aluminum

The kinetic energy of superconducting electrons in an ultrathin, doubly connected superconducting cylinder, determined by the applied flux, increases as the cylinder diameter decreases, leading to a destructive regime around half-flux quanta and a superconductor to normal metal quantum phase transition (QPT). Regular steplike features in resistance versus temperature curves taken at fixed flux values were observed near the QPT in ultrathin Al cylinders. It is proposed that these features are most likely resulting from a phase separation near the QPT in which normal regions nucleate in a homogeneous superconducting cylinder.     

Measuring local optical properties: near-field polarimetry of photonic block copolymer morphology

Ultrahigh molecular weight polystyrene-b-polyisoprene block copolymers (BCs), noted for their photonic behavior, were imaged using transmission near-field scanning optical microscopy (NSOM) and NSOM polarimetry. Our improved scheme for polarization modulation (PM) polarimetry, which accounts for optical anisotropies of the NSOM aperture probe, enables mapping of the local diattenuation and birefringence (with separately aligned diattenuating and fast axes) in these specimens with subdiffraction limited resolution. PM-NSOM micrographs illuminate the mesoscopic optical nature of these BC specimens by resolving individual microphase domains and defect structures.     

Synthesis of pyrazolo[1,5-alpha]pyrimidinone regioisomers

This work describes two distinct routes to prepare pyrazolo[1,5-alpha]pyrimidin-7-ones and two distinct routes to prepare pyrazolo[1,5-alpha]pyrimidin-5-ones. Use of 1,3-dimethyluracil as the electrophile in the preparation of the pyrimidin-5-one regioisomer represents a correction of previously reported results. Also, a novel reaction to prepare this isomer was identified and the reaction mechanism elucidated. This work provides the experimentalist with complimentary synthetic pathways that afford either the pyrimidin-7-one or the pyrimidin-5-one regioisomer.     

Selective nucleophilic chemistry in the synthesis of 5-carbamoyl-3-sulfanylmethylisoxazole-4-carboxylic acids

The solution-phase syntheses of 5-carbamoyl-3-sulfanylmethylisoxazole-4-carboxylic acids were accomplished from dimethyl 3-chloromethylisoxazole-4,5-dicarboxylate by selective nucleophilic chemistry. For example, treatment of this trifunctionalized core with 3-bromobenzylamine and subsequent X-ray analysis identified the sole product as methyl 5-(3-bromobenzylcarbamoyl)-3-chloromethylisoxazole-4-carboxylate. Subjecting this amide/ester to thiophenol in the presence of 1 N NaOH completed the two-step transformation of this versatile starting material to the targeted 5-carbamoyl-3-sulfanylmethylisoxazole-4-carboxylic acid. Employing various amines and thiophenols, this chemistry was applied in the generation of a 90-compound library of druglike isoxazoles.