Catalytic properties of microheterogeneous systems based on cationic surfactants in transesterification processes

The kinetic parameters of the transesterification processes of carboxylic acid esters under the action of alkylphenolates in aqueous micellar solutions of cetyltrimethylammonium bromide (CTAB) are found. The observed catalytic effect is due to a complex mechanism of the solvent effect, which includes a shift of acid-base equilibria in the nucleophile and the formation of mixed CTAB/alkylphenol micelles. The dynamic structure of these aggregates (size, diffusion mobility, and molecular packing density in a surface layer) has been characterized by spin-probe EPR spectroscopy and high-resolution pulsed-field gradient ¹H NMR spectroscopy.     

Quantitation of peptides and proteins by matrix-assisted laser desorption/ionization mass spectrometry using (18)O-labeled internal standards

A method for quantitating proteins and peptides in the low picomole and sub-picomole range has been developed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with internal (18)O-labeled standards. A simple procedure is proposed to produce such internal standards for the tested sample by enzymatic hydrolysis of the same sample (with known concentration) in (18)O-water. A mathematical algorithm was developed which uses the isotopic patterns of the substance, the internal standard, and the substance/internal standard mixture for accurate quantitation of the substance. A great advantages of the proposed method is the absence of molecular weight limitation for the protein quantitation and the possibility of quantitation without previous fractionation of proteins and peptides. Using this strategy, the peptide angiotensinogen and two proteins, RNase and its protein inhibitor, were quantified by MALDI-time-of-flight (TOF) mass spectrometry.