Patterns in the vocalizations of male harbor seals

Comparative analyses of the roar vocalization of male harbor seals from ten sites throughout their distribution showed that vocal variation occurs at the oceanic, regional, population, and subpopulation level. Genetic barriers based on the physical distance between harbor seal populations present a likely explanation for some of the observed vocal variation. However, site-specific vocal variations were present between genetically mixed subpopulations in California. A tree-based classification analysis grouped Scottish populations together with eastern Pacific sites, rather than amongst Atlantic sites as would be expected if variation was based purely on genetics. Lastly, within the classification tree no individual vocal parameter was consistently responsible for consecutive splits between geographic sites. Combined, these factors suggest that site-specific variation influences the development of vocal structure in harbor seals and these factors may provide evidence for the occurrence of vocal dialects.     

The effect of a low-frequency sound source (acoustic thermometry of the ocean climate) on the diving behavior of juvenile northern elephant seals,Mirounga angustirostris

Changes in the diving behavior of individual free-ranging juvenile northern elephant seals, Mirounga angustirostris, exposed to the acoustic thermometry of the ocean climate (ATOC) sound source were examined using data loggers. Data loggers were attached to the animals and measured swim speed, maximum depth of dive, dive duration, surface interval, descent and ascent rate, and descent and ascent angle along with sound pressure level (SPL). The ATOC sound source was at a depth of 939 m and transmitted at 195 dB re: 1 microPa at 1 m centered at 75 Hz with a 37.5-Hz bandwidth. Sound pressure levels (SPL) measured at the seal during transmissions averaged 128 dB and ranged from 118 to 137 dB re: 1 microPa for the 60-90 Hz band, in comparison to ambient levels of 87-107 dB within this band. In no case did an animal end its dive or show any other obvious change in behavior upon exposure to the ATOC sound. Subtle changes in diving behavior were detected, however. During exposure, deviations in descent rate were greater than 1 s.d. of the control mean in 9 of 14 seals. Dive depth increased and descent velocity increased in three animals, ascent velocity decreased in two animals, ascent rate increased in one animal and decreased in another, and dive duration decreased in only one animal. There was a highly significant positive correlation between SPL and descent rate. The biological significance of these subtle changes is likely to be minimal. This is the first study to quantify behavioral responses of an animal underwater with simultaneous measurements of SPL of anthropogenic sounds recorded at the animal.     

Total synthesis of polemannones B and C

The first total synthesis of polemannones B and C, higly oxygenated benzoxanthenones derivatives from Polemannia montana, is reported employing our new catalytic Cu(II)/sparteine system for β,β-phenolic couplings and tandem inverse-electron demand Diels-Alder reaction cascade in 75-90% yield.     

Microdeformation behavior in nanotemplated epoxy thermosets: A study with in situ tensile deformation technique in transmission electron microscopy

Microdeformation behavior in nanostructured block copolymer‐toughened epoxy resins, or templated epoxy thermosets, was studied using an in situ tensile deformation technique performed directly in a transmission electron microscope. The observed microdeformation modes were found to correlate well with the macroscopic mechanical properties of the materials. In the order of decreasing macroscopic fracture toughness, the microdeformation modes were observed to change from large uniform plastic deformation over an extensive area, to localized plastic deformation bands, to little plastic deformation observed in the most brittle material. A similar trend was also observed when samples of the same material were tested at different temperatures, reflecting changes in the deformation mechanism as a function of temperature. Structural defects were observed in nanotoughening phases when plastic deformation was observed. The implication of the observed microdeformation modes to the macroscopic toughening mechanisms is discussed in the context of the micromorphology of the nanometer sized toughening phases and parameters of the epoxy matrix chemistry such as bromination, molecular weight, and interfacial miscibility. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 393–406, 2009     

Measurement of time histories of stable intermediates during first stage ignition of n-heptane and its two isomers in a shock tube

We report the first shock tube measurements of formaldehyde (CH₂O) during the first stage ignition of n-heptane, 2-methylhexane and 3,3-dimethylpentane, in highly diluted fuel/oxygen mixtures in the pressure range of 7–10 atm and temperature range of 700–880 K. Combined time histories of all carbonyl (–C = O) species, CO and fuel were also measured simultaneously in an effort to study the impact of fuel structure on the concentration and the rate of evolution of first stage ignition products. Of the three isomers studied in this work, n-heptane was found to be the fastest, while 3,3-dimethylpentane was found to be the slowest. The differences in the time scale of formation, and plateau concentration of the intermediates between the isomers across the entire range of test conditions suggests a strong dependency of the measured time histories to fuel structure. These species therefore act as markers of the Negative Temperature Coefficient (NTC) behavior of fuels and can be used as targets for developing semi-empirical, hybrid chemistry models of complex, multi-component petroleum derived gasoline and jet fuels. The time histories reported in this work should prove very useful in the refinement of detailed kinetic models of n-heptane, and development of rate rules for branched alkane isomers.     

Mass spectroscopic investigation of bis-1,3-urea calix[4]arenes and their ability to complex N-protected α-amino acids

We report the ability of urea’s appended onto the upper-rim of conformationally locked ‘cone’ calix[4]arenes to show a preference for binding specific N-protected α-amino acids. Superior complexation (as judged by mass spectroscopy) between N-protected α-amino results and bis-1,3-N-benzylureas calix[4]arenes was observed when methylene bridges were present between the calix[4]arene ‘host’ and the urea motif. Interestingly we also demonstrate that subjecting mixtures of structurally diverse N-Fmoc-α-amino acids to a single bis-1,3-N-benzylurea derived calix[4]arene allows, in some cases, the calix[4]arene ‘host’ to selectively ‘pick out’ and complex a specific N-Fmoc amino acid from the mixture.