Proof of formation of an unstable conjugated triene on decomposition of gibberellin A3 in water
It has been shown by the methods of1H NMR and high-performance liquid chromatography with recording of UV spectra that in aqueous solutions of gibberellin A3, via gibberellenic acid, an unstable conjugated triene having λmax 326 nm is formed which is readily converted into allogibberic acid and is isolated as a mixture (1:2) with this acid. In the1H NMR spectrum of the triene, confirming its structure, spin-spin coupling both of the H-5 proton and of the protons of the methyl group with all the H-1, H-2, and the H-3 protons is observed. The precursor of allogibberic acid has been ascribed the structure of (−)-13-hydroxy-19,20-dinorgibberella-1,3,9,16-tetraen-7-oic acid with a conjugated 1,3,9-trienic system.
New intermediates in the aqueous decomposition of gibberellic acid
The decomposition pathway of gibberellic acid (I) through gibberellenic acid (III) in aqueous solution has been investigated. Decomposition of gibberellenic acid in deuterium oxide gives [9-2H]allogibberic acid (V), [9-2H]-9-epi-allogibberic acid (VI), and unlabelled 9,11-didehydroallogibberic acid (IX). Two partially characterised hydroperoxides (XV) and (XVII) have been detected as intermediates in the oxidative transformation of gibberellic acid through gibberellenic acid to 9,11-didehydroallogibberic acid. Mechanisms are proposed on the basis of these results.
Turbulent boundary layer wall‐pressure fluctuations downstream from an abrupt change in surface roughness
Spectra of wall‐pressure fluctuations beneath a turbulent boundary layer have been investigated immediately downstream from an abrupt change in surface roughness, from slightly rough to very rough. Over the measurable frequency band (400 Hz to 7 kHz), the spectra in the first 150 mm scale on wall variables. This indicates that the motions responsible for the pressure fluctuations measured in this region are very close to the wall. Farther downstream this scaling procedure breaks down. It is suggested that the initially thin internal layer behaves independently of the flow external to it until it has grown appreciably and only then interacts with the outer boundary layer. It was found that, for all frequencies measured, the dimensional spectral level decreases initially then rises to a maximum at 250 mm from the roughness change before decreasing once more. The position of the maximum is close to where the internal layer ceases to have a distinct edge.