Lysine peroxycarbamates: free radical-promoted peptide cleavage

Strategies are reported that combine in one step a predictable chemical-based protein digestion with mass spectrometry. Lysine residue amino groups in peptides and proteins are modified by reaction with a peroxycarbonate derived from p-nitrophenol, and tert-butyl hydroperoxide. The peroxycarbonate reacts with lysine residues in peptides and proteins, and the resulting lysine peroxycarbamates undergo homolytic fragmentation under conditions of low-energy collision-induced dissociation (CID). Observed fragmentation of the peptides involves apparent free radical processes including Hofmann-L?ffler-type rearrangements that lead to peptide chain fragmentation. Strategies for directed cleavage of peptides by free radical promoted processes are feasible, and such strategies may well simplify schemes for protein analysis.     

Analysis and interpretation of excess molar properties of amphiphile + water systems : Part 3. Excess molar volumes of isopropoxyethanol + water and isobutoxyethanol + water

Excess molar volumes at 25°C, are reported for the systems isoPrOEtOH + water and isoBuOEtOH + water across their entire composition ranges. These data have been compared to those for their normal alkyl analogs in order to assess the effects of both - and β-chain branching.

The results are discussed in terms of the relative abilities of the amphiphiles to form structured aggregates.     

Commuting point transformations

Summary The question considered is the following: If two invertible measure preserving point transformations commute, in what sense is one a function of the other? The main theorem is the following: If two invertible measure preserving transformations commute, and if the first admits of approximation by periodic transformations, then the second transformation is a piecewise power of the first, where we say that is a piecewise power of if there exists a sequence [j(n)] of positive integers such that for each measurable set A the limit of the measure of the symmetric difference of (A) and ^j(n) (A) tends to zero.Research supported in part by NSF grant GP-3752.