Mammalian laryngseal air sacs add variability to the vocal tract impedance: physical and computational modeling

Cavities branching off the main vocal tract are ubiquitous in nonhumans. Mammalian air sacs exist in human relatives, including all four great apes, but only a substantially reduced version exists in humans. The present paper focuses on acoustical functions of the air sacs. The hypotheses are investigated on whether the air sacs affect amplitude of utterances and/or position of formants. A multilayer synthetic model of the vocal folds coupled with a vocal tract model was utilized. As an air sac model, four configurations were considered: open and closed uniform tube-like side branches, a rigid cavity, and an inflatable cavity. Results suggest that some air sac configurations can enhance the sound level. Furthermore, an air sac model introduces one or more additional resonance frequencies, shifting formants of the main vocal tract to some extent but not as strongly as previously suggested. In addition, dynamic range of vocalization can be extended by the air sacs. A new finding is also an increased variability of the vocal tract impedance, leading to strong nonlinear source-filter interaction effects. The experiments demonstrated that air-sac-like structures can destabilize the sound source. The results were validated by a transmission line computational model.     

Nitrogen stable isotopes reveal age-dependent dietary shift in the Japanese scallop Mizuhopecten yessoensis

Ontogenetic niche shifts in diet are a consequence of changes in body size or resource partitioning between age classes. To better resolve the feeding patterns of the Japanese scallop Mizuhopecten yessoensis, we examined the relative importance of age and size in the diet of this species using stable isotope ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) from 2006 to 2009. Contribution of food sources was quantified using an isotope mixing model by comparing the muscle tissue isotope ratios to those of suspended particulate organic matter (SPOM) and their zooplankton prey (e.g. micro- and meso-zooplankton). Unlike the δ¹³C values, which remained constant with age and size, muscle δ¹⁵N values were more positively correlated with age accounting for 69?% of variations than size with only 46?%. Increasing ¹⁵N values with age suggested that shifts in diet from SPOM to micro- and meso-zooplankton occurred during ontogeny in M. yessoensis. Results of the isotope mixing model indicated that SPOM contribution to scallop’s diet decreased from 68 to 8?% while those of zooplankton increased from 15 to 50?% with increasing age. This study concludes that age-related dietary shift explains the enrichment of ¹⁵N, as a result of predation on zooplankton by M. yessoensis.     

Synthesis of hydroxyoligophenylenes containing electron‐donating,electron‐accepting groups,or π‐deficient aromatic ring and their solvatochromic behavior

We have reported oligo(p‐phenylene)s (OPPs) with an OH group located at one end, namely, OPP(n)‐OHs (where n is the number of benzene rings). The OPPs exhibited significant solvatochromism; the deprotonation of the OH groups of OPP(n)‐OHs , when treated with NaH, caused a bathochromic shift of absorption maxima (λ_max) that increased with the donor numbers (DNs) of the solvents. We assumed that the solvatochromism exhibited by OPP(n)‐ONa was attributed to an intramolecular charge shift from the sodium phenoxy group(s) to the adjacent rings. In this study, to investigate the assumption, hydroxyoligophenylenes ( R‐OPP(n)‐OH ) with an electron‐donating dimethylamino group (n = 3, R = NMe₂), an electron‐accepting nitro group (n = 3, R = NO₂), and a π‐deficient pyridine ring (n = 2, R = Py) were synthesized by the Suzuki coupling reaction. The deprotonation of the OH group of by treatment with NaH caused a bathochromic shift (Δλ) of λ_max of R‐OPP(m)‐ONa . The Δλ of the deprotonated species increased with the DNs of the solvents. The emission peak positions of R‐OPP(m)‐ONa depended on the DNs of the solvents; therefore, the emission color could be tuned by changing the solvent. R‐OPP(m)‐OH received an electrochemical oxidation of the OH group and OPP unit. The data related to the remarkable solvatochromic behavior of R‐OPP(n)‐ONa will be useful information for the development of new luminescent materials.     

Enantioselective addition of diethylzinc to aldehydes catalyzed by 3,3′‐bis(2‐oxazolyl)‐1,1′‐bi‐2‐naphthol (BINOL‐Box) ligands derived from 1,1′‐bi‐2‐naphthol

With 3,3′‐bis(2‐oxazolyl)‐1,1′‐bi‐2‐naphthols (BINOL‐Box) synthesized from 1,1′‐bi‐2‐naphthol (BINOL), the enantioselective addition of diethylzinc to aryl aldehydes proceeded smoothly to give secondary aryl alcohols in good yield with good enantioselectivity. Interestingly, the yields and enantioselectivities were affected by the mixing sequence of the reactants. Furthermore, the synthesis of both enantiomers of the addition products has been achieved using the same ligands by choosing achiral additives, Ti(O‐iPr)₄ and 4A molecular sieves. Copyright © 2000 John Wiley & Sons, Ltd.     

Infrared Spectroscopy and X-Ray Diffraction Studies on the Structure and Thermal Behavior of Biodegradable Polyhydroxyalkanoates

The structure and thermal behavior of new types of bacterial copolyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate); P(HB-co-HHx) (HHx=2.5, 3.4, and 12 mol %) have been explored by means of wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), and infrared (IR) spectroscopy. The WAXD pattern of P(HB-co-HHx) (HHx=12 mol %) copolymer measured at room temperature has revealed that it has an orthorhombic system (α=β=γ=90°) with a=5.76Å, b=13.20Å, c=5.96Å (fiber repeat), which is identical to that of poly(3-hydroxybutyrate) (PHB). It has been found from the temperature-dependent variations of the WAXD pattern that only the a lattice parameter shows the thermal expansion, while the b lattice parameter changes little with temperature in the crystalline P(HB-co-HHx) (HHx=12 mol %). This observation suggests that there are inter and intramolecular interactions between C=O groups and alkyl groups along the a axis and that interactions are broken little by little with temperature. IR spectra were measured for the four kinds of polymers over a temperature range from 30°C to high temperatures (200°C; PHB, 180°C; P(HB-co-HHx) (HHx=2.5 mol %), 180°C; P(HB-co-HHx) (HHx=3.4 mol %), 150°C; P(HB-co-HHx) (HHx=12 mol %)). Temperature-dependent IR spectral variations were analyzed for the CH, C=O, and C-O-C stretching band regions, and bands characteristic of crystalline and amorphous parts were identified in each region. It has been found from the IR study that the strength of interaction between the C=O group and the CH₃ (or CH₂) group is similar among the four polymers and that the population of C=O groups that are not involved in the interaction becomes higher with the increase in HHx. Both WAXD and IR studies have revealed that the crystallinity of P(HB-co-HHx) (HHx=12 mol %) decreases gradually starting from relatively low temperature (about 60°C) while that of PHB remains high up to 170°C.     

Diffusion of Rod-Like Polypeptides in the Liquid Crystalline and Isotropic Phases as Studied by High Field-Gradient NMR Spectroscopy

In this lecture the measurements and analyses of the isotropic and anisotropic diffusion coefficients(D) of rod-like polypeptide such as poly(γ-L-glutamate)(PLG) with n-alkyl side chains, of which the main chain takes the α-helical conformation, as a function of the main chain length in the thermotropic and lyotropic liquid crystalline phases over a wide range of temperatures from 30 to 80°C by means of pulse high field-gradient spin echo ¹H NMR method have been introduced. In the anisotropic diffusion, the D_∥ value in direction parallel to the α-helical chain axis is found to be much larger than the D_⊥ value in direction perpendicular to the α-helical chain axis. The diffusion process is followed by the Kirkwood theory. Further, it is described that the diffusion in the nematic liquid crystalline phase is much slower than that in the isotropic phase.     

Preparation of poly(alkylenebenzimidazole) by ruthenium complex catalyzed polycondensation of 3,3′‐diaminobenzidine with α,ω‐diols

The reactions of 3,3′‐diaminobenzidine with 1,12‐dodecanediol in 1 : 1–1:3 molar ratios in the presence of RuCl₂(PPh₃)₃ catalyst give poly(alkylenebenzimidazole), [ (CH₂)₁₁ O (CH₂)₁₁ Im / (CH₂)₁₀ Im ]_n (Im: 5,5′‐dibenzimidazole‐2,2′‐diyl) (I_a‐I_d) in 71–92% yields. The relative ratio between the [(CH₂)₁₁ O (CH₂)₁₁ Im ] unit (A) and the [‐ (CH₂)₁₀ Im ] unit (B) in the polymer chain varies depending on the ratio of the substrates used. The polymer I_a obtained from the 1 : 3 reaction contains these structural units in a 98 : 2 ratio. The polymers are soluble in polar solvents such as DMF (N,N‐dimethylformamide), DMSO (dimethyl sulfoxide), and NMP (N‐methyl‐2‐pyrrolidone) and have molecular weights M_n (M_w) of 4,200–4,800 (4,800–6,500) by GPC (polystyrene standard). The polymerization of the diol and 3,3′‐diaminobenzidine in higher molar ratios leads to partial cross‐linking of the resulting polymers I_e and I_f via condensation of imidazole NH group with CH₂OH group. Similar reactions of 3,3′‐diaminobenzidine with α,ω‐diols, HO(CH₂)_mOH (m = 4–10), in a 1 : 3 molar ratio give the polymers containing [ (CH₂)_m−1 O (CH₂) _m−1 Im ] and [ (CH₂) _m−2 Im ] units with partial cross‐linked structures. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1383–1392, 1999