Hydrogenation of olefins in supercritical CO(2) catalyzed by palladium nanoparticles in a water-in-CO(2) microemulsion

Nanometer-sized metallic palladium particles can be synthesized by hydrogen reduction of Pd2+ ions dissolved in the water core of a water-in-CO2 microemulsion. The Pd nanoparticles, stabilized by the micromeulsion and uniformly dispersed in the supercritical fluid phase, are effective catalysts for hydrogenation of olefins. Examples of rapid and efficient hydrogenation of water-soluble and CO2-soluble olefins catalyzed by the Pd nanoparticles in supercritical CO2 are given.     

Determination of trace elements in carbonates by instrumental neutron activation analysis

A systematic non-destructive determination of eighteen trace elements (F, Na, Cl, Sc, Mn, Zn, Br, Sr, I, Ba, La, Ce, Sm, Eu, Tb, Yb, Th and U) in carbonate samples by thermal neutron activation analysis was developed. Three 0.2–0.5g samples were irradiated for 15 sec (in the case of determination of F), for 3 min (in the case of Na, Cl, Mn, Sr and I) and for 60 hrs (in the case of Sc, Zn, Br, Ba, La, Ce, Sm, Eu, Tb, Yb, Th and U) in the TRIGA MARK II Reactor at a thermal neutron flux of 5·10¹¹ n·cm⁻²·sec⁻¹ (15 sec and 3 min irradiation) and 1.5·10¹²n·cm⁻²·sec⁻¹ (60 hrs irradiation), respectively. According to the half life of the nuclides formed, the activities were measured with a Ge(Li) spectrometer as follows,²⁰F∶15 sec counting after 20–25 sec cooling,²⁴Na,³⁸Cl,⁵⁶Mn,^87mSr and¹²⁸I∶600 sec couting after 30–120 min cooling,⁸²Br,¹⁴⁰La,¹⁵³Sm,¹⁷⁵Yb and²³⁹Np (daughter of²³⁹U)∶3000 sec counting after 1 week cooling,⁴⁶Sc,⁶⁵Zn,¹³¹Ba,¹⁴¹Ce,¹⁵²Eu,¹⁶⁰Tb and²³³Pa (daughter of²³³Th)∶5000 sec counting after 1 month cooling. The errors due to the fluctuation of the neutron flux and the counting geometry were minimized by the use of calcium determined previously with EDTA-titration as an internal standard. The interferences from²⁴Mg(n, p)²⁴Na and²³⁵U(n, fission) reactions were corrected by the activities produced by the reactions in unit weight of magnesium and uranium, and their concentrations in samples measured experimentally. The data of Na, Mn, Zn and Sr were compared with the results obtained by atomic absorption analysis.     

Catalytic hydrogenation of arenes with rhodium nanoparticles in a water-in-supercritical CO2 microemulsion

Rhodium nanoparticles dispersed by a CO2 microemulsion are effective catalysts for rapid hydrogenation of arenes in supercritical CO2.     

The acoustic bases for gender identification from children's voices.

The purpose of this study was to examine the acoustic characteristics of children's speech and voices that account for listeners' ability to identify gender. In Experiment I, vocal recordings and gross physical measurements of 4-, 8-, 12-, and 16-year olds were taken (10 girls and 10 boys per age group). The speech sample consisted of seven nondiphthongal vowels of American English (/ae/ "had," /E/ "head," /i/ "heed," /I/ "hid," /a/ "hod," /inverted v/ "hud," and /u/ "who'd") produced in the carrier phrase, "Say /hVd/ again." Fundamental frequency (f0) and formant frequencies (F1, F2, F3) were measured from these syllables. In Experiment II, 20 adults rated the syllables produced by the children in Experiment I based on a six-point gender rating scale. The results from these experiments indicate (1) vowel formant frequencies differentiate gender for children as young as four years of age, while formant frequencies and f0 differentiate gender after 12 years of age, (2) the relationship between gross measures of physical size and vocal characteristics is apparent for at least 12- and 16-year olds, and (3) listeners can identify gender from the speech and voice of children as young as four years of age, and with respect to young children, listeners appear to base their gender ratings on vowel formant frequencies. The findings are discussed in relation to the development of gender identity and its perceptual representation in speech and voice.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

From Surface‐Inspired Oxovanadium Silsesquioxane Models to Active Catalysts for the Oxidation of Alcohols with O2—The Cinnamic Acid/Metavanadate System

Silsesquioxane dioxovanadate(V) complexes were investigated with respect to their potential as a catalyst for the oxidative dehydrogenation of alcohols with O₂ as an oxidant. The turnover frequencies determined were comparatively low, but during the oxidation of cinnamic alcohol an increase in activity was observed in the course of the process, which was inspected more closely. It turned out that during the oxidation of cinnamic alcohol, not only was the aldehyde formed but also cinnamic acid, which in turn reacts with the silsesquioxane complex employed to give NBu₄[O₂V(O₂CC₂H₂Ph)₂], which can also be obtained from NBu₄VO₃ and cinnamic acid and represents a far more active catalyst, not only for cinnamic alcohol but also for other activated alcohols and hydrocarbons. The rate‐determining step of the conversion corresponds to an hydrogen‐atom abstraction from the C? H units, as shown by the determination of the kinetic isotope effect in case of 9‐hydroxyfluorene, and the reoxidation of the reduced catalyst proceeds via a peroxo intermediate, which is also capable of oxidizing one alcohol equivalent. Furthermore the influence of the organic residues at the carboxylate ligands on the catalyst performance was investigated, which showed that the activity increases with decreasing pK_s value. Moreover, it was found that during the oxidation the catalyst slowly decomposes, but can be regenerated by addition of excessive carboxylic acid.     

Determination of rare earth elements in recent and fossil shells by radiochemical neutron activation analysis

Seven rare earth elements (La, Ce, Sm, Eu, Tb, Yb and Lu) in marine shell samples were determined by neutron activation analysis. In order to measure γ-ray using a Ge(Li) detector without serious interference from the intense Compton background from²⁴Na, a simple radiochemical separation was performed by a co-precipitation method with hydrated iron(III) oxide. The chemical yields for shell samples (91–99%) were determined by a re-activation technique for Gd and Yb. The interference from the²³⁵U(n, fission) reaction was corrected for determination of La and Ce. The data obtained in this study showed the behavior of rare earth elements in shells during the process of fossilization.     

Revisiting stop-consonant perception for two-formant stimuli

The purpose of this study was to reexamine the factors leading to stop-consonant perception for consonant-vowel (CV) stimuli with just two formants over a range of vowels, under both an open- and closed-response condition. Five two-formant CV stimulus continua were synthesized, each covering a range of second-formant (F2) starting frequencies, for vowels corresponding roughly to [i,I,ae,u,a]. In addition, for the [I] and [a] continua, the duration of the first-formant (F1) transition was systematically varied. Three main findings emerged. First, criterion-level labial and alveolar responses were obtained for those stimuli with substantial F2 transitions. Second, for some stimuli, increases in the duration of the F1 transition increased velar responses to criterion level. Third, the response paradigm had a substantial influence on stop-consonant perception across all vowel continua. The results support a model of stop-consonant perception that includes spectral and time-varying spectral properties as integral components of analysis.     

Tunable picosecond infrared pulses generated by stimulated electronic Raman scattering of a mode-locked Ti:Sapphire laser in potassium vapor

A down-conversion to the mid-infrared region by using Stimulated Electronic Raman Scattering (SERS) in potassium vapor is described. The pump radiation is a frequency-doubled regeneratively amplified Ti:Sapphire laser with a pulse duration of 2 ps, pulse energy of 0.2 mJ, and repetition rate of 10 Hz. With the pumping frequency tuned around the potassium 4s-5p transition, nearly transform-limited infrared radiation tunable between 2.2 and 3.4 m has been generated with a peak infrared energy of 12 µJ, corresponding to a quantum efficiency of 17%, and with a pulse duration of 2 ps. The present tuning range could be extended by extending the tuning range of the pump laser. In comparison, intense infrared radiation of 90 µJ energy but with a very narrow tunability around 2.9 m has also been generated by SERS in barium vapor.