Secondary structure of peptides. 4:13C-Nmr CP/MAS investigation of solid oligo- and poly(L-alanines)

Primary and tertiary amine-initiated polymerizations of L-alanine-N-carboxyanhydride (L-Ala-NCA) were conducted at 20 or 100°C in a variety of solvents. The 75.5-MHz 13C-nmr CP/MAS spectra of the resulting poly(L-alanines) revealed that all samples contain both α-helix and pleated-sheet structures. Depending on the reaction conditions the α-helix content varied between ca. 1 and 99%. Reprecipitation from aprotic nonsolvents does not change the α-helix/β-sheet ratio, indicating that this ratio is thermodynamically controlled. Since relatively large amounts of oligopeptides of degree of polymerization (DP) 4–6 can be extracted by means of acetic acid, it is concluded that (a) most poly(L-alan…

Strukturuntersuchung von polyestern durch direkten abbau im massenspektrometer, 3. Poly-β-propiolacton, poly-β-pivalolacton und poly-δ-valerolacton

Poly(oxycarbonylethylene) (poly-β-propiolactone), poly(oxycarbonyl-1,1-dimeothylethylene) (poly-β-pivalolactone), and poly(oxycarbonyltetramethylene) (poly-δ-valerolactone) were pyrolyzed directly in the ion source of a mass spectrometer and their thermal and electron impact induced degradation mechanisms are established. Poly-β-propiolactone is thermally degraded by rupture of the OCH2-bond by a cis elimination to give carboxyl and acryloyl endgroups, whereas poly-δ-valerolactone depolymerizes to δ-valerolactone. Poly-β-pivalolactone degrades thermally to cyclic oligomers of pivalolactone, which could be proved by a separated pyrolysis and IR-spectroscopy and gel chromatography.

Über den thermischen Abbau von alternierenden Copolyamiden im Massenspektrometer