Solid-state NMR structural studies of the fibril form of a mutant mouse prion peptide PrP89-143(P101L)

The peptide fragment 89-143 of the prion protein (carrying a P101L mutation) is biologically active in transgenic mice when in a fibrillar form. Injection of these fibrils into transgenic mice (expressing full length PrP with the P101L mutation) induces a neurodegenerative prion disease (Kaneko et al., J. Mol. Biol. 295 (2000) 997). Here we present solid-state NMR studies of PrP(89-143)(P101L) fibrils, probing the conformation of residues in the hydrophobic segment 112-124 with chemical shifts. The conformations of glycine residues were analyzed using doubly (13)C=O labeled peptides by two-dimensional (2D) double-quantum correlation, and double-quantum filtered dephasing distance measurements. MQ-NMR experiments were carried out to probe the relative alignment of the individual peptides fibrils. These NMR studies indicate that the 112-124 segment adopts an extended beta-sheet conformation, though not in a parallel, in register alignment. There is evidence for conformational variability at Gly 113. DQ correlation experiments provide useful information in regions with conformational heterogeneity.     

Similarity, uncertainty, and masking in the identification of nonspeech auditory patterns

This study examined whether increasing the similarity between informational maskers and signals would increase the amount of masking obtained in a nonspeech pattern identification task. The signals were contiguous sequences of pure-tone bursts arranged in six narrow-band spectro-temporal patterns. The informational maskers were sequences of multitone bursts played synchronously with the signal tones. The listener's task was to identify the patterns in a 1-interval 6-alternative forced-choice procedure. Three types of multitone maskers were generated according to different randomization rules. For the least signal-like informational masker, the components in each multitone burst were chosen at random within the frequency range of 200-6500 Hz, excluding a "protected region" around the signal frequencies. For the intermediate masker, the frequency components in the first burst were chosen quasirandomly, but the components in successive bursts were constrained to fall in narrow frequency bands around the frequencies of the components in the initial burst. Within the narrow bands the frequencies were randomized. This masker was considered to be more similar to the signal patterns because it consisted of a set of narrow-band sequences any one of which might be mistaken for a signal pattern. The most signal-like masker was similar to the intermediate masker in that it consisted of a set of synchronously played narrow-band sequences, but the variation in frequency within each sequence was sinusoidal, completing roughly one period in a sequence. This masker consisted of discernible patterns but not patterns that were part of the set of signals. In addition, masking produced by Gaussian noise bursts--thought to produce primarily peripherally based "energetic masking"--was measured and compared to the informational masking results. For the three informational maskers, more masking was produced by the maskers comprised of narrow-band sequences than for the masker in which the frequencies were not constrained to narrow bands. Also, the slopes of the performance-level functions for the three informational maskers were much shallower than for the Gaussian noise masker or for no masker. The findings provided qualified support for the hypothesis that increasing the similarity between signals and maskers, or parts of the maskers, causes greater informational masking. However, it is also possible that the greater masking was a consequence of increasing the number of perceptual "streams" that had to be evaluated by the listener.     

Iron modified mesoporous carbon and silica catalysts for methanol decomposition

Iron modified silica and carbon mesoporous materials with similar textural characteristics are compared in methanol decomposition to H₂, CO and CH₄. The influence of the support on the phase composition and reductive properties of the catalysts is studied by M?ssbauer spectroscopy and TPR with hydrogen. This revised version was published online in June 2006 with corrections to the Cover Date.     

Informational masking caused by contralateral stimulation

Although informational masking is thought to reflect central mechanisms, the effects are generally much stronger when the target and masker are presented to the same ear than when they are presented to different ears. However, the results of a recent study by Brungart and Simpson [J. Acoust. Soc. Am. 112, 2985-2995 (2002)] indicated that a speech masker that is presented contralateral to a speech signal can produce substantial amounts of informational masking when a second speech masker is played simultaneously in the same ear as the signal. In this study, we conducted a series of experiments that paralleled those of Brungart and Simpson but used a pure-tone signal and multitone informational maskers in a detection task. Both the signal and the maskers were played as sequences of short bursts in each observation interval. The maskers were arranged in two types of spectrotemporal patterns. One type of pattern, called "multiple-bursts same" (MBS), has previously been shown to produce very large amounts of informational masking while the other type of pattern, called "multiple-bursts different" (MBD), has been shown to produce very small amounts of informational masking. Several conditions of ipsilateral, contralateral, and combined presentation of these maskers were tested. The results showed that presentation of the MBS masker in the contralateral ear produced a substantial amount of informational masking when the MBD masker was simultaneously presented to the ipsilateral ear. The results supported the earlier findings of Brungart and Simpson indicating that listeners are unable to selectively focus their attention on a single ear in some complex dichotic listening conditions. These results suggest that this contralateral masking effect is not restricted to speech and may reflect more general limitations on processing capacity. Further, it was concluded that the magnitude of the contralateral masking effect was related both to the informational masking value of the contralateral masker and the complexity of the stimulus and/or task in the ear in which the signal was presented.     

P-positions in modular extensions to Nim

In this paper, we consider a modular extension to the game of Nim, which we call m-Modular Nim, and explore its optimal strategy. In m-Modular Nim, a player can either make a standard Nim move or remove a multiple of m tokens in total. We develop a winning strategy for all m with 2 heaps and for odd m with any number of heaps.     

Widespread applicability of bacterial cellulose-ZnO-MWCNT hybrid membranes

The novel photoactive membranes have grabbed the attention in the field of environmental protection by employing wastewater treatments and the removal of microorganisms or organic pollutants from wastewater. Here we present a promising self-supported photoactive hybrid membrane for future antimicrobial and water treatment applications. In this study, the efficiency of bacterial cellulose (BC) - zinc oxide (ZnO) - multi walled carbon nanotube (MWCNT) hybrid membranes in the adsorption and photocatalytic degradation of methylene blue (MB) under UV radiation and the removal of Escherichia coli (E. coli) was investigated. It was found that the photocatalytic efficiency is strongly dependent on both the preparation method and the amount of ZnO-MWCNT additives loaded into the hybrid membranes. The characterization of BC-ZnO-MWCNT membranes was done using scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and X-ray micro computed tomography (μCT) to study the morphological and porosity aspect of the prepared-membranes. The promising results of this study could provide a new pathway in the field of photocatalysed-based water treatment technology by the application of hybrid membranes.     

Quantitation and validation of fluoroquinolones in eggs using liquid chromatography/tandem mass spectrometry

Fluoroquinolone antibiotics are labeled for very limited veterinary use for treatment of some animals and pets, but they are not authorized for food animals in Canada, including egg-producing birds. Because they are approved for other animals, however, fluoroquinolones may appear in eggs through off-labeling or accidental use. This method is capable of quantitating and confirming the presence of 4 fluoroquinolones, ciprofloxacin, danofloxacin, enrofloxacin, and sarafloxacin, over the concentration range 1 to 60 microg/kg (ppb) using 2 internal standards, norfloxacin or lomefloxacin. The compounds are extracted with acidic acetonitrile, isolated using Oasis HLB solid-phase extraction, and quantitated by liquid chromatography/tandem mass spectrometry at 2 transitions. The limits of detection (microg/kg) were evaluated from between-day experiments as: ciprofloxacin, 0.22; danofloxacin (m/z 314), 0.32; enrofloxacin, 0.22; and sarafloxacin, 0.31. The values for the decision limit, CCalpha were 0.33, 0.36, 0.30, and 0.45 microg/kg, respectively.     

Second-sphere effects on H2O2 activation by non-heme FeII complexes: role of a phenol group in the [H2O2]-dependent accumulation of FeIVO vs. FeIIIOOH

Redox metalloenzymes achieve very selective oxidation reactions under mild conditions using O₂ or H₂O₂ as oxidants and release harmless side-products like water. Their oxidation selectivity is intrinsically linked to the control of the oxidizing species generated during the catalytic cycle. To do so, a second coordination sphere is used in order to create a pull effect during the activation of O₂ or H₂O₂, thus ensuring a heterolytic O–O bond cleavage. Herein, we report the synthesis and study of a new non-heme Fe^II complex bearing a pentaazadentate first coordination sphere and a pendant phenol group. Its reaction with H₂O₂ generates the classical Fe^IIIOOH species at high H₂O₂ loading. But at low H₂O₂ concentrations, an Fe^IVO species is generated instead. The formation of the latter is directly related to the presence of the 2nd sphere phenol group. Kinetic, variable temperature and labelling studies support the involvement of the attached phenol as a second coordination sphere moiety (weak acid) during H₂O₂ activation. Our results suggest a direct Fe^II → Fe^IVO conversion directed by the 2nd sphere phenol via the protonation of the distal O atom of the Fe^II/H₂O₂ adduct leading to a heterolytic O–O bond cleavage.

A new Fe^II complex with a phenol group attached as a second coordination sphere moiety activates H₂O₂ to yield Fe^IVO following a mechanism reminiscent of peroxidase enzymes.     

(η6‐2‐Bromo‐1,1′‐biphenyl)tricarbonylchromium

The title compound, [Cr(C₁₂H₉Br)(CO)₃], crystallizes in the triclinic space group with close Br⋯Br separations. These contacts, along with several other factors, influence the (Ph)C—C(o‐BrC₆H₄) dihedral angle of 58.82 (6)°. The typical piano‐stool coordination about the Cr atom is in excellent agreement with the results of density functional theory calculations.     

Design of experiments and detailed uncertainty analysis to develop and validate a solid-phase microextraction/gas chromatography–mass spectrometry method for the simultaneous analysis of 16 pesticides in water

A solid-phase microextraction (SPME)/gas chromatography (GC)–mass spectrometry (MS) multiresidue analytical method was developed for 16 pesticides presenting different physicochemical properties including diphenyl ether, triazine, ureas, acetamides, benzofuran, thiocarbamate, pyridine carboxamides, chloronitrile, piperedine, and azoles. Optimization was achieved by means of the design of experiments methodology. Extraction temperature, extraction time, desorption temperature, and NaCl addition were the factors exhibiting the most significant effects on pesticide extraction. Validation was carried out through model adequacy and specificity tests, limits of quantification and detection determination, and full uncertainty assessment on the whole analytical method. Good first- and second-order model adequacy was found for pesticide calibration. LOQs were in the 0.05–0.5 μg L⁻¹ range and specificity recoveries varied from 75% to 140%. These results were considered acceptable for our research purposes on highly concentrated agricultural flows. Uncertainty calculations accounted for several steps: standard preparation, calibration model selection, and use. On average, real sample concentration uncertainties were lower than 10%, indicating that the analytical method performed very well. Its application to 61 real water samples confirmed the presence of some pesticide concentrations in relation to farmer use, whereas other molecules were usually either not detected or not quantified.