Relative contributions of temporal and place pitch cues to fundamental frequency discrimination in cochlear implantees

The effect of the filter bank on fundamental frequency (F0) discrimination was examined in four Nucleus CI24 cochlear implant subjects for synthetic stylized vowel-like stimuli. The four tested filter banks differed in cutoff frequencies, amount of overlap between filters, and shape of the filters. To assess the effects of temporal pitch cues on F0 discrimination, temporal fluctuations were removed above 10 Hz in one condition and above 200 Hz in another. Results indicate that F0 discrimination based upon place pitch cues is possible, but just-noticeable differences exceed 1 octave or more depending on the filter bank used. Increasing the frequency resolution in the F0 range improves the F0 discrimination based upon place pitch cues. The results of F0 discrimination based upon place pitch agree with a model that compares the centroids of the electrical excitation pattern. The addition of temporal fluctuations up to 200 Hz significantly improves F0 discrimination. Just-noticeable differences using both place and temporal pitch cues range from 6% to 60%. Filter banks that do not resolve the higher harmonics provided the best temporal pitch cues, because temporal pitch cues are clearest when the fluctuation on all channels is at F0 and preferably in phase.     

Highly efficient third-order optical nonlinearities in donor-substituted cyanoethynylethene molecules

We investigated the third-order nonlinear optical properties of several donor-substituted cyanoethynylethene molecules in the zero-frequency limit. We observed nonlinearities that are extraordinarily large relative to the small molecular mass of these molecules and that are within a factor of 50 from the fundamental limit. At a wavelength of 1.5 microm, the rotational average of the third-order molecular polarizability is 53 +/- 13 x 10(-48) m5 V(-2) (3.8 x 10(-33) esu) for the best molecule, which corresponds to 1.7 x 10(-48) m5 V(-2) per delocalized electron. The high nonlinear efficiency of these molecules is due to the compact two-dimensional conjugated system and the effective donor-acceptor substitution patterns.     

Coordination and oxidative addition at a low-coordinate rhodium(I) beta-diiminate centre

The reaction of 14e [L(Me)Rh(coe)] (1; L(Me)[double bond]ArNC(Me)CHC(Me)NAr, Ar[double bond]2,6-Me(2)C(6)H(3); coe[double bond]cis-cyclooctene) with phenyl halides and thiophenes was studied to assess the competition between sigma coordination, arene pi coordination and oxidative addition of a C-X bond. Whereas oxidative addition of the C-Cl and C-Br bonds of chlorobenzene and bromobenzene to L(Me)Rh results in the dinuclear species [[L(Me)Rh(Ph)(micro-X)](2)] (X=Cl, Br), fluorobenzene yields the dinuclear inverse sandwich complex [[L(Me)Rh](2)(anti-micro-eta(4):eta(4)-PhF)]. Thiophene undergoes oxidative addition of the C-S bond to give a dinuclear product. The reaction of 1 with dibenzo[b,d]thiophene (dbt) in the ratio 1:2 resulted in the formation of the sigma complex [L(Me)Rh(eta(1)-(S)-dbt)(2)], which in solution dissociates into free dbt and a mixture of the mononuclear complex [L(Me)Rh(eta(4)-(1,2,3,4)-dbt)] and the dinuclear complex [[L(Me)Rh](2)(micro-eta(4)-(1,2,3,4):eta(4)-(6,7,8,9)-dbt)]. The latter could be obtained selectively by the 2:1 reaction of 1 and dbt. Reaction of 1 with diethyl sulfide produces [L(Me)Rh(Et(2)S)(2)], which in the presence of hydrogen loses a diethyl sulfide ligand to give [L(Me)Rh(Et(2)S)(H(2))] and catalyses the hydrogenation of cyclooctene.     

Tandem addition of trialkyl phosphites to alpha,beta-unsaturated imines: a comparison with silylated phosphites

Trialkyl phosphites were evaluated for addition reactions to alpha,beta-unsaturated imines. An acidic medium is required to allow consecutive 1,4- and 1,2-addition to occur. In this manner, 3-phosphonyl-1-aminophosphonates, phosphonic acid analogues of glutamate, are obtained in good yields (32-90%). The reaction is mainly influenced by the steric bulk of the nitrogen substituent: less steric N-substituents lead to better yields of the tandem adducts.     

Synthesis of 4-phosphono-β-lactams via phosphite addition to acyliminium salts

4-Aryl-4-phosphono-β-lactams are prepared by acylation of iminium salts with chloroacetyl chloride followed by phosphite addition and ring closure using sodium hydride as a base. Deacylation of the iminium salt is in competition with the desired addition of phosphites to acyliminium salts, which lowers the yield of the reaction.     

Synthesis of tricyclic phosphonopyrrolidines via IMDAF: experimental and theoretical investigation of the observed stereoselectivity

During the synthesis of tricyclic phosphonopyrrolidines via intramolecular Diels-Alder reactions of 1-acylamino(furan-2-yl)methyl phosphonates, two isomers are formed in most cases. The presence of a short three-atom tether together with spectroscopic data, including difference NOE, revealed that the cycloaddition occurred exo, but the phosphonate substituent on the tether had an exo or endo orientation. This was confirmed via X-ray analysis. A thermodynamic preference for the product with the phosphonate function in the endo position was observed experimentally and was confirmed theoretically. Density functional theory methods and several high-level post Hartree-Fock procedures were used to rationalize the observed isomer ratio of the IMDAF-reactions. This was done for two different types of reagents: with the activating carbonyl group in the tether or as a substituent on the tether. For the first type of molecules there is a large steric hindrance of the bulky tether substituents that disfavors the exo-isomer. In the latter case, there was a very small energy difference between the transition states causing a mixture of epimers being formed.     

Horizontal localization with bilateral hearing aids: without is better than with

This paper studies the effect of bilateral hearing aids on directional hearing in the frontal horizontal plane. Localization tests evaluated bilateral hearing aid users using different stimuli and different noise scenarios. Normal hearing subjects were used as a reference. The main research questions raised in this paper are: (i) How do bilateral hearing aid users perform on a localization task, relative to normal hearing subjects? (ii) Do bilateral hearing aids preserve localization cues, and (iii) Is there an influence of state of the art noise reduction algorithms, more in particular an adaptive directional microphone configuration, on localization performance? The hearing aid users were tested without and with their hearing aids, using both a standard omnidirectional microphone configuration and an adaptive directional microphone configuration. The following main conclusions are drawn. (i) Bilateral hearing aid users perform worse than normal hearing subjects in a localization task, although more than one-half of the subjects reach normal hearing performance when tested unaided. For both groups, localization performance drops significantly when acoustical scenarios become more complex. (ii) Bilateral, i.e., independently operating hearing aids do not preserve localization cues. (iii) Overall, adaptive directional noise reduction can have an additional and significant negative impact on localization performance.