Sentence recognition in noise promoting or suppressing masking release by normal-hearing and cochlear-implant listeners

Normal-hearing (NH) listeners maintain robust speech understanding in modulated noise by "glimpsing" portions of speech from a partially masked waveform--a phenomenon known as masking release (MR). Cochlear implant (CI) users, however, generally lack such resiliency. In previous studies, temporal masking of speech by noise occurred randomly, obscuring to what degree MR is attributable to the temporal overlap of speech and masker. In the present study, masker conditions were constructed to either promote (+MR) or suppress (-MR) masking release by controlling the degree of temporal overlap. Sentence recognition was measured in 14 CI subjects and 22 young-adult NH subjects. Normal-hearing subjects showed large amounts of masking release in the +MR condition and a marked difference between +MR and -MR conditions. In contrast, CI subjects demonstrated less effect of MR overall, and some displayed modulation interference as reflected by poorer performance in modulated maskers. These results suggest that the poor performance of typical CI users in noise might be accounted for by factors that extend beyond peripheral masking, such as reduced segmental boundaries between syllables or words. Encouragingly, the best CI users tested here could take advantage of masker fluctuations to better segregate the speech from the background.     

Optical Thin-Film Sensors for the Determination of Aqueous Halide Ions

Fourteen thin-film optical sensors in which halide-sensitive fluorophores are immobilized in a thin copolymer film (50 m, dry) have been developed and characterized. The sensor films use rhodamine, 6-methoxyquinoline, and harmane dyes which have been functionalized and bound to a hydrophilic copolymer. The sensor films are reversibly capable of determining aqueous bromide and iodide with 4 and 2% accuracy, respectively, at concentrations of around 10^–3 mol dm^–3, and are more sensitive than previous plastic sensor fabrications. The 90% response time to molar iodide is 30–60 s. A combination of sensor films allows the simultaneous determination of both I^– and Br^– in a mixed-halide solution. The interference of several ions, including pseudo-halides, on the sensor films has been studied.     

How Dihalogens Catalyze Michael Addition Reactions

We have quantum chemically analyzed the catalytic effect of dihalogen molecules (X₂=F₂, Cl₂, Br₂, and I₂) on the aza‐Michael addition of pyrrolidine and methyl acrylate using relativistic density functional theory and coupled‐cluster theory. Our state‐of‐the‐art computations reveal that activation barriers systematically decrease as one goes to heavier dihalogens, from 9.4 kcal mol^?1 for F₂ to 5.7 kcal mol^?1 for I₂. Activation strain and bonding analyses identify an unexpected physical factor that controls the computed reactivity trends, namely, Pauli repulsion between the nucleophile and Michael acceptor. Thus, dihalogens do not accelerate Michael additions by the commonly accepted mechanism of an enhanced donor–acceptor [HOMO(nucleophile)–LUMO(Michael acceptor)] interaction, but instead through a diminished Pauli repulsion between the lone‐pair of the nucleophile and the Michael acceptor's π‐electron system.     

How Divalent Cations Interact with the Internal Channel Site of Guanine Quadruplexes

The formation of guanine quadruplexes (GQ) in DNA is crucial in telomere homeostasis and regulation of gene expression. Pollution metals can interfere with these DNA superstructures upon coordination. In this work, we study the affinity of the internal GQ channel site towards alkaline earth metal (Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺), and (post-)transition metal (Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺) cations using density functional theory computations. We find that divalent cations generally bind to the GQ cavity with a higher affinity than conventional monovalent cations (e. g. K⁺). Importantly, we establish the nature of the cation-GQ interaction and highlight the relationship between ionic and nuclear charge, and the electrostatic and covalent interactions. The covalent interaction strength plays an important role in the cation affinity and can be traced back to the relative stabilization of cations’ unoccupied atomic orbitals. Overall, our findings contribute to a deeper understanding of how pollution metals could induce genomic instability.     

Some comments on the mechanism of the preparation of (Et4N)2B10H10 by thermolysis of Et4NBH4

The volatile intermediate Et₃NBH₃ was isolated during the thermolysis of Et₄NBH₄ at 185°C for 16 hr under dynamic vacuum. The rate of decomposition of Et₄NBH₄ was studied. Separate thermolyses of Et₄NBH₄ (or Et₃NBH₃) with closo B₉H₉^2?nido B₉H^?₁₂, or arachno B₉H₁₄^? did not produce B₁₀H₁₀^2? as the major product. These results are inconsistent with the “build-up” mechanism previously proposed for the thermolytic convertion of BH ₄^? to B₁₀H₁₀^2? and a new mechanism is required.     

Conditions for deuterium exchange mediated by iridium complexes formed in situ

A series of iridium-based complexes formed in situ, containing pyridine, phosphines, triphenylarsine, triphenylstibine, and triphenylamine as ligands, has been screened for ability to mediate ortho-exchange of hydrogen in a series of model substrates. Improved incorporation into a number of substrate classes has been achieved. The electronic properties and number of ligands at the metal centre are instrumental in determining which catalysts are best suited to exchange in any given substrate.