Reacquisition of contrastive stress in an adventitiously deaf speaker using a single-channel cochlear implant

Acoustic correlates of contrastive stress, i.e., fundamental frequency (F0), duration, and intensity, and listener perceptions of stress, were investigated in a profoundly deaf subject (RS) pre/post single-channel cochlear implant and longitudinally, and compared to the overall patterns of age-peer profoundly deaf (JM) and normally hearing subjects (DL). The stimuli were a group of general American English words in which a change of function from noun to verb is associated with a shift of stress from initial to final syllable, e.g., CON'trast versus conTRAST'. Precochlear implant, RS was unable to produce contrastive stress correctly. Hearing one day post-stimulation resulted in significantly higher F0 for initial and final stressed versus unstressed syllables. Four months post-stimulation, RS maintained significantly higher F0 on stressed syllables, as well as generalization of significantly increased intensity and longer syllable duration differences for all stressed versus unstressed syllables. Perceptually, listeners judged RS's contrastive stress placement as incorrect precochlear implant and as always correct post-cochlear implant. JM's contrastive stress was judged as 96% correct, and DL's contrastive stress placement was 100% correct. It was concluded that RS reacquired all acoustic correlates needed for appropriate differentiation of contrastive stress with longitudinal use of the cochlear implant.     

Properties of the 69 150 Tm81 6− β-decaying isomer

Decay experiments for¹⁴⁸Ho 6^? and¹⁵⁰Tm 6^? were carried out at the GSI On-line mass separator using 5 MeV/A⁵⁸Ni-beams on⁹⁴Mo and⁹⁶Ru targets. Gammaγ-andγX-coincidences established the¹⁵⁰Tm 6^? decay scheme, and e^? gave firm I ^π assignments for¹⁴⁸Dy and¹⁵⁰Er levels fed in the decays. It was found that the previously unknown 6 ₁ ^? state in¹⁵⁰Er receives significantβ-strength, which strongly suggestsπh _11/2 νs ₁ ^2/?1 character for the¹⁵⁰Tm 6^? isomer. The results are discussed in terms of the expected GT strength function. Shell model calculations for theπh ₁₁ ^2/4 yrast states are presented.     

Decay properties of ground-state and isomer of 103In

The β-decay properties of ground-state and isomer of ¹⁰³In were investigated by means of γ-ray spectroscopy. The half-lives of ^103g In and ^103m In were determined to be 60 ± 1 s and 34 ± 2 s, respectively. Out of 149 γ transitions ascribed to the decay of ^103g In, 104 have been placed in a decay scheme including 55 excited states of ^103g Cd. The main part of the resulting distribution of the Gamow-Teller strength B(GT) is associated with the feeding of ¹⁰³Cd levels at excitation energies around 3 MeV. This observation can be interpreted as a sign of dominant feeding of three-quasiparticle states in ¹⁰³Cd, which correspond to the 1⁺(πg _9/2 ^?1 , vg_7/2)?πg_9/2 shell-model configuration spread over many levels. The sum of the B(GT) values deduced from the present γ-ray data amounts to 0. 34, which provides a lower limit to the total Gamow-Teller strength. The B(GT) distribution for ¹⁰³In decay is compared to the corresponding experimental results for ^105,107,109In and to theoretical predictions for ^99,101In. The latter were calculated by using an advanced spherical shell model. The β-branching ratio for the ^103m In decay is estimated and compared with the relevant values for the neighbouring indium isotopes including ¹⁰¹In whose half-life was determined to be 14. 9 ± 1.2 s.     

A molecular oyster: a neutral anion receptor containing two cyclopeptide subunits with a remarkable sulfate affinity in aqueous solution

An artificial anion receptor is presented, in which two cyclohexapeptide subunits containing l-proline and 6-aminopicolinic acid subunits in an alternating sequence are connected via an adipinic acid spacer. This compound was devised to stabilize the 2:1 sandwich-type anion complexes that are observed when the two cyclopeptide moieties are not covalently connected and to obtain a 1:1 stoichiometry for these aggregates. Electrospray ionization mass spectrometry and NMR spectroscopic investigations showed that the bridged bis(cyclopeptide) does indeed form defined 1:1 complexes with halides, sulfate, and nitrate. ROESY NMR spectroscopy and molecular modeling allowed a structural assignment of the sulfate complex in solution. The stabilities of various anion complexes were determined by means of NMR titrations and isothermal titration microcalorimetry in 50% water/methanol. Both methods gave essentially the same quantitative results, namely stability constants that varied in the range 105-102 M-1 and decreased in the order SO42- > I- > Br- > Cl- > NO3-. This order was rationalized in terms of the size of the anions with the larger anions forming the more stable complexes because they better fit into the cavity of the host. The ability of sulfate to form stronger hydrogen bonds to the NH groups of the receptor, in addition to its slightly larger ionic radius with respect to iodide, causes the higher stability of the sulfate complex. No significant effect of the countercation on complex stability was observed. Furthermore, complex stability is enthalpically as well as entropically favored. A comparison of the iodide and sulfate complex stabilities of the ditopic receptor with those of a cyclopeptide that forms 1:1 anion complexes in solution showed that the presence of a second binding site increases complex stability by a factor of 100-350.     

A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes

A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi* orbital upon electronic excitation from the singlet ground state S0 to the first excited singlet state S1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S1 state and approaches its minimum structure in the S1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These protonated thiolate functionalities bring protons close to the dinitrogen moiety. Because protonation does not change the pi*-antibonding character of the LUMO, the universal and well-directed character of the photochemical activation process makes it possible to protonate the dinitrogen complex before it is irradiated. The pi*-antibonding LUMO plays the central role in the activation process, since the diazenoid structure was obtained by excitation from various occupied orbitals as well as by a direct two-electron reduction (without photochemical activation) of the complex; that is, the important bending of N2 towards a diazenoid conformation can be achieved by populating the pi*-antibonding LUMO.     

Formation of a Hydroxo-bridged Dinuclear Ru(III)/Ru(III) Complex from N-Methylimidazole and [Ru Cp(CH 3CN) 3] +

The reaction of [RuCp(CH₃CN)₃]PF₆ with 1 equiv of N-Me-imidazole results in the quantitative formation of [RuCp(¹N-N-Me-imidazole)(CH₃CN)₂]PF₆ (1) featuring a ¹N rather than a ¹C bound N-Me-imidazole ligand. According to DFT/B3LYP calculations, ¹N coordination of N-Me-imidazole is preferred over ¹C coordination by 25.5kJ/mol. Upon exposure to air 1 reacts with oxygen and water to afford the novel hydroxo-bridged dinuclear complex of [Ru₂Cp₂(¹N-N-Me-imidazole)₂(-OH)₂](PF₆)₂ (2) featuring a metal-metal single bond. The dimeric nature of 2 was confirmed by a single-crystal X-ray structure analysis.     

Cytokine production after helium-neon laser irradiation in cultures of human peripheral blood mononuclear cells.

The effects of laser light on the immune system have not been extensively characterized. Low-power laser sources, such as the helium-neon (He-Ne) laser with a wavelength of 632.8 nm, have been found to produce photobiological effects with evidence of interference with immunological functions. We have investigated the effects of He-Ne laser irradiation on Ficoll-Hypaque-isolated human peripheral blood mononuclear cells (PBMC). Cultured cells were irradiated for various times at two selected intensities and then stimulated with different mitogens. The rate of incorporation of 3H-thymidine into the DNA of stimulated cells decreased with increasing energy density. The levels of interleukin-1 alpha (IL-1 alpha), interleukin-2 (IL-2), tumour necrosis factor-alpha (TNF-alpha) and interferon-gamma (IFN-gamma) in supernatants of the cultures were determined (irradiated either before or after stimulation). When stimulating cells after irradiation, significantly increased levels of all cytokines were detected after 30 min of irradiation (18.9 J cm-2), whereas after 60 min of irradiation (37.8 J cm-2) cytokine levels were found to be significantly decreased.