Utilizing Experiment and Theory to Evaluate Rhodamine B ethylenediamine as a Fluorescent Sensor for G-type Nerve Agents

Nerve gas mimic binding with Rhodamine B ethylenediamine (1) was studied in organic media. Binding of the nerve gas mimic, diethyl chlorophosphate (DCP), with the probe generated a non-fluorescent intermediate and a fluorescent product. Fluorescent and non-fluorescent products generated were identified using mass spectrometry and X-ray crystallography. Time-dependent density functional theory calculations were also used to investigate the electronic structure of the fluorescent probe in the ground and lowest lying π?→?π* singlet excited state. Though good agreement between theory and experiment can be obtained for the intense peak in the experimental spectrum using non-hybrid functionals, care must be taken when modelling these complexes due to the appearance of an n?→?π* transition that is too low in energy and appears to fall in the shoulders of the π?→?π* transitions.

     

Gap detection thresholds as a function of tonal duration for younger and older listeners.

Twenty normal hearing younger and twenty older adults in the early stages of presbycusis, but with relatively normal hearing at 2 kHz, were asked to discriminate between the presence versus absence of a gap between two equal-duration tonal markers. The duration of each marker was constant within a block of trials but varied between 0.83 and 500 ms across blocks. Notched-noise, centered at 2 kHz, was used to mask on- and off-transients. Gap detection thresholds of older adults were markedly higher than those of younger adults for marker durations of less than 250 ms but converged on those of younger adults at 500 ms. For both age groups, gap detection thresholds were independent of audiometric thresholds. These results indicate that older adults have more difficulty detecting a gap than younger adults when short marker durations (i.e., durations characteristic of speech sounds) are employed. It is shown that these results cannot be explained by linear models of temporal processing but are consistent with differential adaptation effects in younger and older adults.     

Effect of age on detection of gaps in speech and nonspeech markers varying in duration and spectral symmetry

Gap detection thresholds for speech and analogous nonspeech stimuli were determined in younger and older adults with clinically normal hearing in the speech range. Gap detection thresholds were larger for older than for younger listeners in all conditions, with the size of the age difference increasing with stimulus complexity. For both ages, gap detection thresholds were far smaller when the markers before and after the gap were the same (spectrally symmetrical) compared to when they were different (spectrally asymmetrical) for both speech and nonspeech stimuli. Moreover, gap detection thresholds were smaller for nonspeech than for speech stimuli when the markers were spectrally symmetrical but the opposite was observed when the markers were spectrally asymmetrical. This pattern of results may reflect the benefit of activating well-learned gap-dependent phonemic contrasts. The stimulus-dependent age effects were interpreted as reflecting the differential effects of age-dependent losses in temporal processing ability on within- and between-channel gap detection.     

Molybdenum(V) on an oxide string. Formation and solution stability of the linear complex (mu-trans-dioxo(tetraphenylporphyrinato)molybdenato(V))- bis(oxo(tetraphenylporphyrinato)molybdenum(V)) perchlorate

The unusual linear trinuclear complex [Mo3O4(TPP)3]+ is formed in solution upon the reaction of [MoO(TPP)-(OClO3)] with [[MoO(TPP)]2O], and an equilibrium between [Mo3O4(TPP)3]+ and its constituent species is rapidly established. Spectrophotometric experiments suggest that [Mo3O4(TPP)3]+ is the predominant species found in solutions resulting from the mixture of [MoO(TPP)(OClO3)] and [[MoO(TPP)]2O], and its formation is strongly favored (log K = 5.5 +/- 0.5 M-1). No evidence of higher oligomers has been observed. A mechanism for the formation of [Mo3O4(TPP)3]+ by the controlled hydrolysis of [MoO(TPP)(OClO3)] is proposed.