In situ migration of tritiated water and iodine in Grimsel granodiorite,part II: assessment of the diffusion coefficients by TDD modelling

Diffusive transport of iodine (I) and tritiated water (HTO) in granodiorite is studied in the framework of the long term diffusion project (LTD) at the Grimsel Test Site, Switzerland. In this paper we modelled the tracer profiles measured in a long term (780 days) in situ diffusion test was carried out as part of LTD. The main outcome of the modelling tends to prove that the in situ apparent diffusion coefficients of I and HTO are close to the reference apparent diffusion coefficient determined in the laboratory (D _a = 3 × 10⁻¹⁰ m² s⁻¹).

     

Quantum phases for a generalized harmonic oscillator

An effective Hamiltonian for the generalized harmonic oscillator is determined by using squeezed state wavefunctions. The equations of motion over an extended phase space are determined and then solved perturbatively for a specific choice of the oscillator parameters. These results are used to calculate the dynamic and geometric phases for the generalized oscillator with this choice of parameters.      

Soft almost disjoint families

An almost disjoint family is said to be soft if there is an infinite set that meets each in a nonempty but finite set. We consider the associated cardinal invariant defined to be the minimal cardinality of an almost disjoint family that is not soft. We show that this cardinal coincides with J. Brendle's cardinal .

     

Pure-tone threshold estimation from extrapolated distortion product otoacoustic emission I/O-functions in normal and cochlear hearing loss ears

A new method for direct pure-tone threshold estimation from input/output functions of distortion product otoacoustic emissions (DPOAEs) in humans is presented. Previous methods use statistical models relating DPOAE level to hearing threshold including additional parameters e.g., age or slope of DPOAE I/O-function. Here we derive a DPOAE threshold from extrapolated DPOAE I/O-functions directly. Cubic 2 f1-f2 distortion products and pure-tone threshold at f2 were measured at 51 frequencies between f2=500 Hz and 8 kHz at up to ten primary tone levels between L2=65 and 20 dB SPL in 30 normally hearing and 119 sensorineural hearing loss ears. Using an optimized primary tone level setting (L1 = 0.4L2 + 39 dB) that accounts for the nonlinear interaction of the two primaries at the DPOAE generation site at f2, the pressure of the 2 f1-f2 distortion product pDP is a linear function of the primary tone level L2. Linear regression yields correlation coefficients higher than 0.8 in the majority of the DPOAE I/O-functions. The linear behavior is sufficiently fulfilled for all frequencies in normal and impaired hearing. This suggests that the observed linear functional dependency is quite general. Extrapolating towards pDP=0 yields the DPOAE threshold for L2. There is a significant correlation between DPOAE threshold and pure-tone threshold (r=0.65, p<0.001). Thus, the DPOAEs that reflect the functioning of an essential element of peripheral sound processing enable a reliable estimation of cochlear hearing threshold up to hearing losses of 50 dBHL without any statistical data.     

Humans detect gaps in broadband noise according to effective gap duration without additional cues from abrupt envelope changes

Previous studies of behavior and IC single units in the mouse support theoretical expectations that gaps with ramped trailing markers have reduced detectability compared to equivalent gaps with ramped leading markers. In experiment 1, detection probability and response speeds of humans listening for gaps in broadband noise were investigated by independently varying either leading marker fall-time (FT) or trailing marker rise-time (RT). Gaps with silent duration of 1, 4, or 12 ms were presented 2 s into a 3-s noise burst, with either abrupt marker onsets and offsets or linearly ramped RT/FT of 2, 4, or 8 ms durations. Addition of a nonzero RT or FT to the gap silent period increased detectability and also increased reaction speed on trials with "Yes" response, but there was no difference in detectability or response speeds between RT and FT conditions. Experiment 2 extended this finding to gaps having two, one, or no abrupt marker edges. These findings suggest that human listeners do not make use of abrupt onset or offset information to enhance gap detection, but seem to rely on the effective sound level reduction associated with the gap for detection.     

The attention filter for tones in noise has the same shape and effective bandwidth in the elderly as it has in young listeners

Listeners asked to detect tones masked by noise hear frequent signals but miss infrequent probes, suggesting that they attend to spectral regions where they expect the signals to occur. The narrow detection pattern centered on the frequent target approximates that obtained in notched noise, indicating that attention is focused on the auditory filter. We measured attention bands in young and elderly listeners (n=5, 4; 20-25 and 62-82 years of age) for targets (800 or 1200 Hz) and infrequent probe signals (target +/-25-100 Hz) masked in wideband noise. We anticipated that their width would increase with age, as has been reported for auditory filters. A yes-no single-interval procedure provided detection probabilities and detection response speeds. Both measures showed near-linear declines with decreasing signal level, and graded decay functions as probe frequency deviated from the target frequency. Probes deviating from the target by 25 to 50 Hz were equivalent to a 2-dB reduction in signal level for both measures. The equivalent rectangular bandwidth (ERB) for detection approximated 11% of the signal frequency for each age group. Confidence intervals (95%) showed that the elderly ERB could be at most only about 20% larger than that of younger listeners.     

Oxidizing species in the mechanism of cytochrome P450

This review discusses the mechanisms of oxygen activation by cytochrome P450 enzymes, the possible catalytic roles of the various iron--oxygen species formed in the catalytic cycle, and progress in understanding the mechanisms of hydrocarbon hydroxylation, heteroatom oxidation, and olefin epoxidation. The focus of the review is on recent results, but earlier work is discussed as appropriate. The literature through to February 2002 is surveyed, and 175 referenced are cited.     

Twistophane macrocyles with integrated 6,6'-connected-2,2'-bipyridine units: a new lead class of fluorescence sensors for metal ions

The new twistophane macrocycles 2 and 3 have been synthesised; these compounds are composed of a cyclically conjugated dehydrobenzoannulene framework that incorporates 6,6'-connected-2,2'-bipyridine moieties for the purpose of coordinating metal ions. The cyclophanes were characterised by spectroscopic techniques, and shown by molecular mechanics calculations to be helically twisted and chiral molecules that may exist in several possible ground state conformations. UV/vis spectroscopic studies revealed that 2, 3 and precursor 9 bind with different selectivities to particular members of the following small group of metal analytes: CuII, AgI, HgII, Tl1 and PdII. Significantly, 2, 3 and 9 signal the presence of CuII ions through fluorescence emission quenching output responses. Furthermore, cyclophane 3 exhibited a particularly sensitive protontriggered chromogenic fluorescence response. With respect to their unique structural features, high analyte selectivity coupled with their enhanced and characteristic fluorescence emission responses, these molecules are among the first examples representing a new lead class of chemosensory materials. Compounds 2, 3 and 9 and derivatives thereof may, therefore, be expected to find many future applications in the detection of metal-based environmental pollutants, biologically important trace elements and monitoring proton fluxes.     

1H NMR detection of immobilized water molecules within a strong distal hydrogen-bonding network of substrate-bound human heme oxygenase-1

Solution 1H NMR is used to probe the environments of the donor protons of eight strong hydrogen bonds on the distal side of the heme substrate in the cyanide-inhibited, substrate-bound complex of human heme oxygenase, hHO. It is demonstrated that significant magnetization transfer from the bulk water signal to the eight labile protons does not result from chemical exchange, but from direct nuclear Overhauser effect due to the dipolar interaction of these labile protons with "ordered" water molecules. The enzyme labile proton to water proton distances are estimated at approximately 3 A. It is proposed that the role of the strong hydrogen-bonding network is to immobilize numerous water molecules which both stabilize the activated hydroperoxy species and funnel protons to the active site.