SummaryN-terminal protein acetylation is common in eukaryotes and halophilic archaea, but very rare in bacteria. We demonstrate that some of the most abundant proteins present in the crenarchaeote Sulfolobus solfataricus, including subunits of the thermosome, proteosome and ribosome, are acetylated at the N-terminus. Modification was observed at the N-terminal residues serine, alanine, threonine and methionine-glutamate. A conserved archaeal protein, ssArd1, was cloned and expressed in Escherichia coli, and shown to acetylate the same N-terminal sequences in vitro. The specific activity of ssArd1 is sensitive to protein structure in addition to sequence context. The crenarchaeota and euryarchaeota apparently differ in respect of the frequency of acetylation of Met-Glu termini, which appears much more common in S. solfataricus. This sequence is acetylated by the related Nat3 acetylase in eukarya. ssArd1 thus has a relaxed sequence specificity compared with the eukaryotic N-acetyl transferases, and may represent an ancestral form of the enzyme. This represents another example where archaeal molecular biology resembles that in eukaryotes rather than bacteria.

The nitrosocarbonyl arenes or -alkanes, obtained by oxidation of hydroxamic acids, behave as dienophiles towards cyclopentadiene to give the bridged oxazines 1. In the case of pivalo-hydroxamic acid, however, the nitrosocarbonyl compound also reacts as a heterodiene, giving, as well as the oxazine 1d, the 1,4,2-dioxazine 2d; 1d is not converted into 2d under the conditions of the oxidation reaction.Extended heating of compounds 1 slowly converts them into 2 and other more complex reaction products. This contrasts with the rapid and quantitative isomerization of the analogous azodicarbonyl adducts, and probably reflects the lesser crowding of the reacting NCOR group by an adjacent oxygen than by an adjacent NCOR group.1,4-Dimethyl-2,3-diphenylcyclopentadiene traps the nitroso compounds to form the labile oxazines 8, which rapidly isomerize to the dioxazines 9 on brief heating or in polar solvents. In the case of the benzoyl compound 8a the isomerization to 9a is reversible in benzene at 80 °C, favouring the latter isomer by a factor of about 9:1.

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