PubMed Health⌕ Search

Biomedical subjects

J Wronka

Publications and source records attributed to J Wronka.

2 recordsLinked to original sources

Electrophore mass tag dideoxy DNA sequencing.

Toward a goal of dideoxy sequencing DNA utilizing electrophore labels, we prepared four electrophore-labeled DNA oligonucleotide primers. Each primer has a different electrophore and DNA sequence but a common glycol keto (alpha,beta-dihydroxyketo) release group. Cleavage of this latter group by either periodate oxidation or a thermal retroaldol reaction releases the electrophores for detection by mass spectrometry. Successful sequencing data with these primers was obtained by capillary electrophoresis on an ABI Model 310 after fluorescence dideoxy terminator cycle sequencing reactions were conducted. In a separate experiment, it was demonstrated that a cocktail of the four electrophore DNA primers could be detected as a dried sample spot by CO2 laser desorption/capillary collection/gas chromatography electron capture mass spectrometry. These results establish some feasibility for our long-term goal of high-speed multiplex electrophore mass tag dideoxy DNA sequencing. Ultimately we plan to use a higher number of electrophore mass tags and to rely on direct detection of the desorbed electrophores by electron capture time-of-flight mass spectrometry.

Chromatography, High Pressure Liquid↗

Deprotonation reactions of multiply protonated ubiquitin ions.

The gas-phase deprotonation reactions of multiply protonated ubiquitin ions have been studied in a Fourier-transform ion cyclotron resonance mass spectrometer. Electrospray ionization was used to generate ubiquitin ions with attachment of 7-13 protons. Rate constants were measured for the reactions of these protein ions with four amines: n-propylamine, di-n-propylamine, tri-n-propylamine, and N,N,N',N'-tetramethyl-1,4-diaminobutane. The gas-phase basicities of the amines ranged from 210.1 kcal/mol to 232.6 kcal/mol. The rate constants were found to increase as the charge state of the ion increased and as the basicity of the amine increased. Several reactions proceed at near the collision rate and have rate constants in excess of 10(-8) cm3 molecule-1 s-1. With the more basic reactants, multiple protons could be stripped sequentially from ubiquitin ions at roughly equivalent rates, suggesting that these protons are attached to sites with similar basicities. In general, deprotonation occurs if the gas-phase basicity of the amine is within 10 kcal/mol of the intrinsic gas-phase basicity of the amino acid residue being deprotonated. For [M+nH]n+, n = 4-6, nonlinear pseudo-first-order kinetic behavior indicated the presence of multiple ion structures. Kinetic, structural and thermodynamic aspects of these reactions are discussed.

Amines↗