Energetic and spectral properties of triple photon downconversion in a phase-matched KTiOPO4 crystal

We measured the spectrum and energy of infrared triple photons generated in a phase-matched KTiOPO4 crystal pumped by picosecond beams at 532 and 1662 nm. The experimental data are in good agreement with our model, taking into account the spectral linewidths of the incident beams as well as a parasitic Kerr effect.     

Prestress effects on the eigenfrequencies of the soundboards: experimental results on a simplified string instrument

This paper presents an experimental study of the effects of prestresses on the vibration behavior of string instruments. These prestresses are created by gluing ribs (crowning) and tensioning string (downbearing). The effects of these prestresses were previously studied numerically for a piano soundboard by Mamou-Mani et al. [J. Acoust. Soc. Am. 123, 2401-2406 (2008)] and analytically for simplified models by Mamou-Mani et al. [Acta Acust. Unit. Acust. 95, 915-926 (2009)]. In the present study, a specified test bench is designed, including a simplified soundboard (a rectangular plate), a bridge, and a single string. The plate is subjected to in-plane and transverse loads. Vibrational eigenmodes are identified using nearfield acoustical holography (NAH) measurement. The evolution of eigenfrequencies with these specific prestresses is studied. The results show the effectiveness of NAH for this purpose and a very good qualitative concordance with previous numerical and analytical calculus.     

Investigating the consistency of woodwind instrument manufacturing by comparing five nominally identical oboes

For large-scale woodwind instrument makers, producing instruments with exactly the same playing characteristics is a constant aim. This paper explores manufacturing consistency by comparing five Howarth S10 student model oboes. Psychophysical testing involving nine musicians is carried out to investigate perceived differences in the playing properties of the two Howarth oboes believed to be most dissimilar. Further testing, involving one musician and combinations of the five oboes, provides information regarding the relative playabilities of the instruments at specific pitches. Meanwhile, input impedance measurements are made on the five oboes for fingerings throughout the playing range and their bore profiles are measured. The main findings are (1) the two instruments used in the preliminary psychophysical testing are perceived as identical by most of the musicians, although differences are identified by two players when playing the note F6 and by one player when playing in the lowest register, (2) a variation in the playability of F6 across the five oboes is due to differences in the elevation of the C key, and (3) variations in the playing properties in the lowest register are related to input impedance differences,which, in turn, appear to be at least partly due to bore profile differences.     

On the approximation of total absorption of the street open ceiling at low frequencies

This work deals with numerical modeling of sound propagation in street canyons with flat building facades. The street is seen as an open waveguide and two 3D wave models are used: a parabolic equation model and a modal expansion model. The comparison between the models shows a very good agreement. Then, the study focuses on the radiation condition at the opening of the street. In usual energetic approaches as ray tracing, the opening is assumed to be perfectly absorbing. This assumption is realistic at high frequencies, however the reflection phenomenon caused by the geometric discontinuity at the opening is still an open question at low frequencies. This possible reflection is investigated through three parametric studies of the acoustic longitudinal energy flux decay along the street. The first study shows that the approximation of total absorption at the street open ceiling is no longer valid when the ratio η between the street width and the wavelength is small. The second study shows that the effect of source height is weak except under restrictive conditions: when η is small and when the source height is not small compared to the wavelength, the approximation of total absorption is acceptable for an elevated source. At least, the results of the last study show that the error made by assuming a perfectly absorbing ceiling is not negligible compared to the error made by considering perfectly reflecting walls.     

The Taming of Redox-Labile Phosphidotitanocene Cations

Tame d⁰ phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d¹ precursors with [Cp₂Fe][BPh₄]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d⁰ complexes, whereas dπ–pπ repulsion prevents such interactions in the d¹ complexes. In addition, CH–π interactions were observed in several complexes, both in solution and in the solid state, between the phosphido ligand and the phosphane arm. The d⁰ complexes were found to be light sensitive, and decompose through Ti−P bond homolysis to give Ti^III species. A naked d⁰ phosphidotitanocene cation has been trapped by reaction with diphenylacetylene, yielding a Ti/P frustrated Lewis pair (FLP), which was found to be less reactive than a previously reported Zr analog.     

Decoupled Mild Solutions of Path-Dependent PDEs and Integro PDEs Represented by BSDEs Driven by Cadlag Martingales

Potential Analysis - We focus on a class of path-dependent problems which include path-dependent PDEs and Integro PDEs (in short IPDEs), and their representation via BSDEs driven by a cadlag...     

Sweeping total reflection X-ray fluorescence optimisation to monitor the metallic contamination into IC manufacturing

Among the methods available on the market today to control as metallic contamination in integrated circuit manufacturing, Sweeping Total reflection X-ray Fluorescence mode appears a very good method, providing fast and entire wafer mapping. With the goal of a pertinent use of Sweeping Total reflection X-ray Fluorescence in advanced Integrated Circuit manufacturing this work discusses how acceptable levels of contamination specified by the production (low levels to be detected) can be taken into account.     

Reactant concentrations from fluorescence correlation spectroscopy with tailored fluorescent probes. An example of local calibration-free pH measurement

The present account is concerned with the measurement of local reactant concentrations by observing specific fluorescent probes in fluorescence correlation spectroscopy (FCS). The Theoretical Analysis section revisits the photophysical, thermodynamic, and kinetic information that is contained in the corresponding FCS correlation curves. In particular, we examine the conditions under which FCS is revealed as a superior tool to measure concentrations of reactive species. Careful molecular engineering of the specific fluorescent probes that simultaneously integrates photophysical, thermodynamic, and kinetic constraints will be required to benefit most from FCS. We illustrate the FCS titration approach with a series of fluorescent probes that we tailored to measure pH at around 4-6 by FCS after two-photon excitation. We show that an optimal design allows one to access pH without any preliminary calibrations such as the determination of the protonation constant or the photophysical properties of the fluorescent probe.     

Dendrimers with Porphyrin Cores: Synthetic models for globular heme proteins

Dendritic iron porphyrins were synthesized as functional mimics of globular electron-transfer heme proteins. The cascade molecules 1 · Zn ? 3 Zn of first to third generation were obtained starting from the (meso-diarylporphyrin) zinc 6 · Zn which contains four carboxylate arms for attachment of the poly(ether-amide) dendritic branches by peptide-coupling methodology (Scheme 1). Generation 3 compound 3 · Zn with 108 methyl-carboxylate end groups has a molecular weight of 19054. D, and computer modeling suggests that its structure is globular and densely-packed, measuring ca. 4 nm in diameter and, therefore, similar in dimensions to the electron-transfer protein cytochrome-c. Starting from the generation 1 poly(carboxylic acid) 11 · Zn and the generation 2 analog 12 · Zn the dendritic Zn^II porphyrins 4 · Zn and 5 · Zn , respectively, were obtained by esterification with triethyleneglycol monomethyl ether (Schemes 3 and 4). Demetallation followed by insertion of Fe^II and in situ oxidation afforded the water-soluble dendritic iron porphyrins 4 FeCl and 5 FeCl . The electrochemical behavior of esters 1 · Zn ? 3 · Zn in organic solvents changed smoothly with increasing dendritic generation (Table 1). Progressing from 1 · Zn to 3 · Zn in THF, the first porphyrin-centered oxidation and reduction potentials become more negative by 320 and 210mV, respectively. These changes were attributed to strong microenvironmental effects imposed on the electroactive core by the densely packed dendritic surroundings. The electrochemical properties of 4 · FeCl and 5 · FeCl were investigated by cyclic voltammetry in both CH₂Cl₂ and H₂O (Tables 2 and 3). Progressing from 4 · FeCl to 5 · FeCl in CH₂Cl₂, the redox potential of the biologically relevant Fe^III/Fe^II couple remained virtually unchanged, whereas in aqueous solution, 5 FeCl exhibited a potential 420 mV more positive than did 4 FeCl. The large difference between these potentials in H₂O was attributed to differences in solvation of the core electrophore. Whereas the relatively open dendritic branches in 4 · Fecl do not impede access of bulk solvent to the central core, the densely packed dendritic superstructure of 5 · FeCl significantly reduces contact between the heme and external solvent. As a result, the more charged Fe^III state is destabilized relative to Fe^II, and the redox potential is strongly shifted to a more positive value.     

Design, synthesis, structure, and gas (N2, Ar, CO2, CH4, and H2) sorption properties of porous metal-organic tetrahedral and heterocuboidal polyhedra

A strategy based on assembling metal ions and organic carboxylate links has been applied for the design and synthesis of a new class of porous, truncated tetrahedral and heterocuboidal polyhedra, whose pore size and functionality can be systematically varied. The synthesis of this series of metal-organic polyhedra (MOPs) employs sulfate-capped oxygen-centered iron-carboxylate trimers, Fe3O(CO2)3(-)(SO4)3, as rigid nodes separated by linear (phenyl, biphenyl, terphenyl, and tetrahydropyrene) or trigonal (benzenetriphenyl) links to yield five highly crystalline polyhedra of general formula [NH2(CH3)2]8[Fe12O4(-)(SO4)12(link)x(py)12].G (x = 6 for linear or 4 for trigonal, py = pyridine, G = guests). In this series, the size of each polyhedron has been varied from 20.0 to 28.5 A (on edge), and the corresponding pore diameter from 7.3 to 13.3 A. Gas sorption isotherms were measured for three members of this series to reveal significant uptake of gases (N2, Ar, CO2, H2, CH4) and benzene and exhibit Type I sorption behavior that is indicative of permanent porosity. The apparent surface areas for these compounds range from 387 to 480 m(2)/g.