Frequency discrimination of complex tones; assessing the role of component resolvability and temporal fine structure

Thresholds for discriminating the fundamental frequency (FO) of a complex tone, FODLs, are small when low harmonics are present, but increase when the number of the lowest harmonic, N, is above eight. To assess whether the relatively small FODLs for N in the range 8-10 are based on (partly) resolved harmonics or on temporal fine structure information, FODLs were measured as a function of N for tones with three successive harmonics which were added either in cosine or alternating phase. The center frequency was 2000 Hz, and N was varied by changing the mean FO. A background noise was used to mask combination tones. The value of FO was roved across trials to force subjects to make within-trial comparisons. N was roved by +/- 1 for every stimulus, to prevent subjects from using excitation pattern cues. FODLs were not influenced by component phase for N= 6 or 7, but were smaller for cosine than for alternating phase once N exceeded 7, suggesting that temporal fine structure plays a role in this range. When the center frequency was increased to 5000 Hz, performance was much worse for low N, suggesting that phase locking is important for obtaining low FODLs with resolved harmonics.     

Effects of level and frequency on the audibility of partials in inharmonic complex tones

The effect of level and frequency on the audibility of partials was measured for complex tones with partials uniformly spaced on an equivalent rectangular bandwidth (ERB(N)) number scale. On each trial, subjects heard a sinusoidal "probe" followed by a complex tone. The probe was mistuned downwards or upwards (at random) by 4.5% from the frequency of one randomly selected partial in the complex. The subject indicated whether the probe was higher or lower in frequency than the nearest partial in the complex. The frequencies were roved from trial to trial, keeping frequency ratios fixed. In experiment 1, the level per partial, L, was 40 or 70 dB SPL and the mean frequency of the central partial, f(c), was 1201 Hz. Scores for the highest and lowest partials in the complexes were generally high for all spacings. Scores for the inner partials were close to chance at 0.75-ERB(N) spacing, and improved as the spacing was increased up to 2 ERB(N). For intermediate spacings, performance was better for the lower level used. In experiment 2, L was 70 dB SPL and f(c) was 3544 Hz. Performance worsened markedly for partial frequencies above 3544 Hz, consistent with a role of phase locking.     

Isolating the energetic component of speech-on-speech masking with ideal time-frequency segregation

When a target speech signal is obscured by an interfering speech wave form, comprehension of the target message depends both on the successful detection of the energy from the target speech wave form and on the successful extraction and recognition of the spectro-temporal energy pattern of the target out of a background of acoustically similar masker sounds. This study attempted to isolate the effects that energetic masking, defined as the loss of detectable target information due to the spectral overlap of the target and masking signals, has on multitalker speech perception. This was achieved through the use of ideal time-frequency binary masks that retained those spectro-temporal regions of the acoustic mixture that were dominated by the target speech but eliminated those regions that were dominated by the interfering speech. The results suggest that energetic masking plays a relatively small role in the overall masking that occurs when speech is masked by interfering speech but a much more significant role when speech is masked by interfering noise.     

The influence of N-substitution on the reductive elimination behaviour of hydrocarbyl-palladium-carbene complexes--a DFT study

The reductive elimination of 2-hydrocarbyl-imidazolium salts from hydrocarbyl-palladium complexes bearing N-heterocyclic carbene (NHC) ligands represents an important deactivation route for catalysts of this type. We have explored the influence that carbene N-substituents have on both the activation energy and the overall thermodynamics of the reductive elimination reaction using density functional theory (DFT). Given the proximity of the N-substituent to the three-centred transition structure, steric bulk has little influence on the activation barrier and it is electronic factors that dominate the barriers' magnitude. Increased electron donation from the departing NHC ligand acts to stabilise the associated complex against reductive elimination, with stability following the trend: Cl < H < Ph < Me < Cy < iPr < neopentyl < tBu. The intimate involvement of the carbene p pi-orbital in determining the barrier to reductive elimination means N-substituents that are capable of removing pi-density (e.g. phenyl) act to promote a more facile reductive elimination.     

Triarylphosphine-stabilized platinum nanoparticles in three-dimensional nanostructured films as active electrocatalysts

Ligand-stabilized platinum nanoparticles (Pt NPs) can be used to build well-defined three-dimensional (3-D) nanostructured electrodes for better control of the catalyst architecture in proton exchange membrane fuel cells (PEMFCs). Platinum NPs of 1.7 +/- 0.5 nm diameter stabilized by the water-soluble phosphine ligand, tris(4-phosphonatophenyl)phosphine (TPPTP, P(4-C6H4PO3H2)3), were prepared by ethylene glycol reduction of chloroplatinic acid and subsequent treatment of the isolated nanoparticles with TPPTP. The isolated TPPTP-stabilized Pt NPs were characterized by multinuclear magnetic resonance spectroscopy (31P and 195Pt NMR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). The negatively charged TPPTP-Pt NPs were electrostatically deposited onto a glassy carbon electrode (GCE) modified with protonated 4-aminophenyl functional groups (APh). Multilayers were assembled via electrostatic layer-by-layer deposition with cationic poly(allylamine HCl) (PAH). These multilayer films are active for the key hydrogen fuel cell reactions, hydrogen oxidation (anode) and oxygen reduction (cathode). Using a rotating disk electrode configuration, fully mass-transport limited kinetics for hydrogen oxidation was obtained after 3 layers of TPPTP-Pt NPs with a total Pt loading of 4.2 microg/cm2. Complete reduction of oxygen by four electrons was achieved with 4 layers of TPPTP-Pt NPs and a total Pt loading of 5.6 microg/cm2. A maximum current density for oxygen reduction was reached with these films after 5 layers resulting in a mass-specific activity, i(m), of 0.11 A/mg(Pt) at 0.9 V. These films feature a high electrocatalytic activity and can be used to create systematic changes in the catalyst chemistry and architecture to provide insight for building better electrocatalysts.     

Measuring charge transport from transient photovoltage rise times. A new tool to investigate electron transport in nanoparticle films

Charge transport rate at open-circuit potential (V(oc)) is proposed as a new characterization method for dye-sensitized (DS) and other nanostructured solar cells. At V(oc), charge density is flat and measurable, which simplifies quantitative comparison of transport and charge density. Transport measured at V(oc) also allows meaningful comparison of charge transport rates between different treatments, temperatures, and types of cells. However, in typical DS cells, charge transport rates at V(oc) often cannot be measured by photocurrent transients or modulation techniques due to RC limitations and/or recombination losses. To circumvent this limitation, we show that charge transport at V(oc) can be determined directly from the transient photovoltage rise time using a simple, zero-free-parameter model. This method is not sensitive to RC limitation or recombination losses. In trap limited devices, such as DS cells, the comparison of transport rates between different devices or conditions is only valid when the Fermi level in the limiting conductor is at the same distance from the band edge. We show how to perform such comparisons, correcting for conduction band shifts using the density of states (DOS) distribution determined from the same photovoltage transients. Last we show that the relationship between measured transport rate and measured charge density is consistent with the trap limited transport model.     

Andreev states near short-ranged pairing potential impurities

We study Andreev states near atomic scale modulations in the pairing potential in both s- and d-wave superconductors with short coherence lengths. For a moderate reduction of the local gap, the states exist only close to the gap edge. If one allows for local sign changes of the order parameter, however, resonances can occur at energies close to the Fermi level. The local density of states (LDOS) around such pairing potential defects strongly resembles the patterns observed by tunneling measurements around Zn impurities in Bi2Sr2CaCu2O8+x (BSCCO). We discuss how this phase impurity model of the Zn LDOS pattern can be distinguished from other proposals experimentally.     

Scale dependence of branching in arterial and bronchial trees

Although models of branching in arterial and bronchial trees often predict a dependence of bifurcation parameters on the scale of the bifurcating vessels, direct verification of this dependence by comparison with data is uncommon. We compare measurements of bifurcation parameters of airways and arterial trees of different mammals as a function of scale to general features predicted by theoretical models based on minimization of pumping power and network volume. We find that the size dependence is more complex than existing theories based solely on energy and volume minimization explain, and suggest additional factors that may govern the branching at different scales.     

0-pi transitions in Josephson junctions with antiferromagnetic interlayers

We show that the dc Josephson current through superconductor-antiferromagnet-superconductor (S-AF-S) junctions manifests a remarkable atomic-scale dependence on the interlayer thickness. At low temperatures the junction is either a 0 or pi junction depending on whether the AF interlayer consists of an even or odd number of atomic layers. This is associated with different symmetries of the AF interlayers in the two cases. In the junction with odd AF interlayers an additional pi- 0 transition can take place as a function of temperature. This originates from the interplay of spin-split Andreev bound states. Experimental implications of these theoretical findings are discussed.     

Phospholipid biotinylation of polydimethylsiloxane (PDMS) for protein immobilization

Polydimethylsiloxane (PDMS) surfaces can be functionalized with biotin groups by adding biotinylated phospholipids to the PDMS prepolymer before curing. The addition of beta-D-dodecyl-N-maltoside (DDM) in the solution blocks non-specific protein binding on these functionalized PDMS surfaces. We characterize the surface by measuring fluorescently labeled streptavidin binding. Single molecule tracking shows that the phospholipids are not covalently linked to PDMS polymer chains, but the surface functionalization is not removed by washing. We demonstrate the immobilization of biotinylated antibodies and lectins through biotin-avidin interactions.