Sound localization of stereo reproduction with parametric loudspeakers

A parametric loudspeaker radiates an audible signal by the interaction of the primary wave that is amplitude modulated and is known as a super-directivity loudspeaker. The parametric loudspeaker is one of the prominent applications of nonlinear acoustics. So far, the applications have been limited monaural reproduction sound system for public address in museum, station, street etc. In this paper, we investigated sound localization of stereo reproduction using two parametric loudspeakers in comparison with that using two ordinary dynamic loudspeakers. In subjective tests, the binaural information ILD (Interaural Level Difference) or ITD (Interaural Time Delay) was focused on. To investigate the characteristics of sound localization in a wide listening area, three typical listening positions were picked up. Signals were 500 Hz, 1 kHz, 2 kHz and 4 kHz pure tones and pink noise. The used parametric loudspeaker was an equilateral hexagon. The subjective test led to the results that when the parametric loudspeakers were used, the listeners at the three typical listening positions perceived the correct sound localization of not only pure tone but also pink noise and when the ordinary dynamic loudspeakers were used, except for the case of pure tone with ITD, the tendency was almost similar to those using the parametric loudspeakers. The second subjective tests were conducted in order to investigate in details the difference between parametric loudspeakers and ordinary dynamic loudspeakers by increasing the number of subjects. In the case of ITD and 500 Hz using the ordinary dynamic loudspeakers, three types of sound localization were categorized, in which the reversed type was major and the normal and the other types were minor. The ILDs which were measured with a dummy head and were calculated with several formulas were almost the same and indicated the reasons of the reversed typed sound localization and a serious influence of the crosstalk. It was found that in the case of pure tone with ITD, the contradiction between the binaural information ILD and ITD is remarkable, because the directivity of the ordinary dynamic loudspeakers was so dull that the crosstalk components had a serious influence on sound localization. It was determined the parametric loudspeaker could transmit correct binaural information to the listener, because the directivity of the parametric loudspeakers was so sharp that it suppressed the cross talk components.     

Pulsed electron spin nutation spectroscopy of weakly exchange-coupled biradicals: a general theoretical approach and determination of the spin dipolar interaction

Weakly exchange-coupled biradicals have attracted much attention in terms of their DNP application in NMR spectroscopy for biological systems or the use of synthetic electron-spin qubits. Pulse-ESR based electron spin nutation (ESN) spectroscopy applied to biradicals is generally treated as transition moment spectroscopy from the theoretical side, illustrating that it is a powerful and facile tool to determine relatively short distances between weakly exchange-coupled electron spins. The nutation frequency as a function of the microwave irradiation strength ω(1) (angular frequency) for any cases of weakly exchange-coupled systems can be classified into three categories; D(12) (spin dipolar interaction)-driven, Δg-driven and ω(1)-driven nutation behaviour with the increasing strength of ω(1). For hetero-spin biradicals, Δg effects can be a dominating characteristic in the biradical nutation spectroscopy. Two-dimensional pulse-based electron spin nutation (2D-ESN) spectroscopy operating at the X-band can afford to determine small values of D(12) in weakly exchange-coupled biradicals in rigid glasses. The analytical expressions derived here for ω(1)-dependent nutation frequencies are based on only four electronic spin states relevant to the biradicals, while real biradical systems often have sizable hyperfine interactions. Thus, we have evaluated nuclear hyperfine effects on the nutation frequencies to check the validity of the present theoretical treatment. The experimental spin dipolar coupling of a typical TEMPO-based biradical 1, (2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2)]piperidin-N-oxyl-4-yl)(2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2),(15)N]piperidin-(15)N-oxyl-4-yl) terephthalate in a toluene glass, with a distance of 1.69 nm between the two spin sites is D(12) = -32 MHz (the effect of the exchange coupling J(12) is vanishing due to the homo-spin sites of 1, i.e.Δg = 0), while 0 < |J(12)|≦ 1.0 MHz as determined by simulating the random-orientation CW ESR spectra of 1. In addition, we have carried out Q-band pulsed ELDOR (ELectron-electron DOuble Resonance) experiments to confirm whether the obtained values for D(12) and J(12) are accurate. The distance is in a fuzzy region for the distance-measurements capability of the conventional, powerful ELDOR spectroscopy. The strong and weak points of the ESN spectroscopy with a single microwave frequency applicable to weakly exchange-coupled multi-electron systems are discussed in comparison with conventional ELDOR spectroscopy. The theoretical spin dipolar tensor and exchange interaction of the TEMPO biradical, as obtained by sophisticated quantum chemical calculations, agree with the experimental ones.     

Development of soft-based double-stranded peptide chelators which selectively separate europium and lanthanum ions based on the hardness concept

New double-stranded peptide chelators (1) conjugated Cat (2,3-dihydroxybenzoic acid) were synthesized and formed a molecular complex 1-Eu(3+) (or 1-Lu(3+)) with Eu(3+) and Lu(3+) but not La(3+). The double-stranded peptide chelator may prove to be useful tools for studying the selective separation of lanthanide ions.     

Pyrene-sensitized electron transport across vesicle bilayers: Dependence of transport efficiency on pyrene substituents

Endoergic electron transport across vesicle bilayers from ascorbate (Asc-) in the inner waterpool to methylviologen (MV2+) in the outer aqueous solution was driven by the irradiation of pyrene derivatives embedded in the vesicle bilayers. The initial rate of MV2+ reduction is dependent on the substituent group of the pyrenyl ring; a hydrophilic functional group linked with the pyrenyl ring by a short methylene chain acts as a sensitizer for the electron transport. Mechanistic studies using (1-pyrenyl)alkanoic acids (1a-c) as sensitizers suggest that the electron transport is mainly initiated by the reductive quenching of the singlet excited state of the pyrene by Asc- and proceeds by a mechanism involving electron exchange between the pyrenes located at the inner and outer interface across the vesicle bilayer. We designed and synthesized novel unsymmetrically substituted pyrenes having both a hydrophilic group linked by a short methylene chain and a hydrophobic long alkyl group (5a-c), which acted as excellent sensitizers for the electron transport across vesicle bilayers.     

Perception and production boundaries between single and geminate stops in Japanese

The theory of relational acoustic invariance [Pickett, E. R., et al. (1999). Phonetica 56, 135-157] was tested with the Japanese stop quantity distinction in disyllables spoken at various rates. The questions were whether the perceptual boundary between the two phonemic categories of single and geminate stops is invariant across rates, and whether there is a close correspondence between the perception and production boundaries. The durational ratio of stop closure to word (where the "word" was defined as disyllables) was previously found to be an invariant parameter that classified the two categories in production, but the present study found that this ratio varied with different speaking rates in perception. However, regression and discriminant analyses of perception and production data showed that treating stop closure as a function of word duration with an intercept term represented the perception and production boundaries very well. This result indicated that the durational ratio of adjusted stop closure (i.e., closure with an added constant) to the word was invariant and distinguished the two phonemic categories clearly. Taken together, the results support the relational acoustic invariance theory, and help refine the theory with regard to exactly what form 'invariance' can take.     

Synthesis and properties of through‐space conjugated polymers based on π–π stacked 1,3‐biarylpropane tethering units

Novel skipped‐π polymers in which the π‐components are connected with 2‐substituted trimethylene tethering units exhibit bathochromically shifted, broadened ultraviolet absorption with a unique lower‐energy absorption band and a largely red‐shifted fluorescent emission. These results suggest that through‐space π–π interactions owing to a stair‐like stacking substructure in these polymers extend the π‐conjugation of the components in the ground and excited states. As the photophysical properties of the polymers observed both in a solution and in a dried film are similar to those of the J‐aggregates of π‐molecules, these polymers may be considered as pseudo J‐stacking (or J‐like‐stacking) polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3412–3419     

Current-dependent linewidth of a spin-transfer nano-oscillator

Power spectra of a spin-transfer nano-oscillator, in which a reflection layer is included, are measured for current densities up to 1.2×10⁷ A/cm². A clear oscillation peak, which is slightly asymmetric with respect to the peak frequency, is observed at 5 GHz under the external field of 700 Oe. The large red shift of the peak frequency on increasing the current, which has been reported in nano-contact devices, is not observed. The relatively low oscillation frequencies as well as the absence of the large red shift indicate the reduction in the demagnetizing field in the free layer. The linewidth decreases with the current and is inversely proportional to the square of the precession amplitude of magnetization in accordance with the recent linear theories.     

Maximum principle for fully nonlinear equations via the iterated comparison function method

We present various versions of generalized Aleksandrov–Bakelman–Pucci (ABP) maximum principle for L ^p -viscosity solutions of fully nonlinear second-order elliptic and parabolic equations with possibly superlinear-growth gradient terms and unbounded coefficients. We derive the results via the “iterated” comparison function method, which was introduced in our previous paper (Koike and Święch in Nonlin. Diff. Eq. Appl. 11, 491–509, 2004) for fully nonlinear elliptic equations. Our results extend those of (Koike and Święch in Nonlin. Diff. Eq. Appl. 11, 491–509, 2004) and (Fok in Comm. Partial Diff. Eq. 23(5–6), 967–983) in the elliptic case, and of (Crandall et al. in Indiana Univ. Math. J. 47(4), 1293–1326, 1998; Comm. Partial Diff. Eq. 25, 1997–2053, 2000; Wang in Comm. Pure Appl. Math. 45, 27–76, 1992) and (Crandall and Święch in Lecture Notes in Pure and Applied Mathematics, vol. 234. Dekker, New York, 2003) in the parabolic case. Dedicated to Hitoshi Ishii on the occasion of his 60th birthday.     

Organic polyanionic high-spin molecular clusters: topological-symmetry controlled models for organic ferromagnetic metals

Trianionic spin-quartet and tetraanionic spin-quintet molecular clusters derived from m-dibenzoylbenzene in solution were identified by CW-ESR/pulse-ESR based two-dimensional electron spin transient nutation spectroscopy, and their spin and clustering structures in the ground state were determined in terms of a D-tensor based phenomenological approach and DFT calculations. The molecular structures obtained semiempirically are supported by DFT-based quantum chemical calculations. The DFT calculations have been tested for a sodium ion bridged fluorenone-based cluster, [fluorenone(-)˙ {Na(+)(dme)(2)}](2), whose crystal structure was reported in the literature [H. Bock, H.-F. Herrmann, D. Fenske and H. Goesmann, Angew. Chem., Int. Ed. Engl., 1988, 27, 1067], reproducing the experimentally determined moelcular structure of the dimer cluster. It is suggested that both the quartet and quintet clusters in the 2-MTHF glass and solution form the cross-typed structures with the two m-dibenzoylbenzene moieties in cis-configuration. A dianionic spin-triplet m-dibenzoylbenzene derivative was detected for the first time and its charge and spin densities were studied by the quantum chemical calculations. The high-spin states of the open-shell entities under study were confirmed by X-band pulse-ESR based electron spin nutation spectroscopy in organic frozen glasses. The D values and other spin Hamiltonian parameters of all the polyanionic high-spin species were determined by the hybrid eigenfield spectral simulation for fine-structure ESR spectra. m-Dibenzoylbenzene provides pseudo-degenerate π-LUMOs arising from its topological symmetry of the π-electron network and its dianion in the triplet ground state is a prototypical model for topologically-controlled genuinely organic ferromagnetic metals.