RESUMO
One of the most challenging fundamental problems in establishing prebiotically plausible routes for phosphorylation reactions using phosphate is that they are thermodynamically unfavorable in aqueous conditions. Diamidophosphate (DAP), a potentially prebiotically relevant compound, was shown to phosphorylate nucleosides in aqueous medium, albeit at a very slow rate (days/weeks). Here, we demonstrate that performing these reactions within an aerosol environment, a suitable model for the early Earth ocean-air interface, yields higher reaction rates when compared to bulk solution, thus overcoming these rate limitations. As a proof-of-concept, we demonstrate the effective conversion (~6.5-10%) of uridine to uridine-2',3'-cyclophosphate in less than 1 h. These results suggest that aerosol environments are a possible scenario in which prebiotic phosphorylation could have occurred despite unfavorable rates in bulk solution.
RESUMO
A high-resolution method of spectral analysis, of the class generally called "maximum entropy method," was used in a study of aortic porcine valve closing sounds in 37 patients (ages 19 to 76). Spectra from 27 normal xenografts, implanted from 2 weeks to 61 months previously, were characterized by a dominant frequency peak, F1, at 89 +/- 15 Hz (mean +/- SD), with a lower amplitude peak, F2, at 154 +/- 25 Hz. Eight of nine patients with aortic porcine valve dysfunction were proved surgically to have leaflet degeneration or infection and had either F1 (139 +/- 54 Hz) and/or F2 (195 +/- 74 Hz) significantly higher than normal (p less than .001). In two patients with paravalvar leak but no leaflet abnormality, F1 and F2 were in the normal range. Estimation of F1 and F2 was highly reproducible and was unaffected by duration of implant up to 5 years. Spectral analysis of aortic porcine valve closing sounds by the maximum entropy method may be useful for detection of intrinsic xenograft dysfunction.