RESUMO
The CH-stretching vibrational CD (VCD) spectra of glycyl-L-alanine, L-alanylglycine, and L-alanyl-L-alanine have been studied at neutral, high, and low pH in D2O solution. The intense positive VCD band attributed to the C alpha H stretch of the alanyl residue in glycyl-L-alanine at neutral pH is absent in L-alanylglycine. In contrast to the VCD spectra of L-alanine, the positive methine-stretching VCD band in glycyl-L-alanine and L-alanyl-L-alanine is still present at pH 2. Based on the ring current mechanism, the VCD spectra are consistent with the presence of a five-membered CO...HN intramolecular hydrogen-bonded ring between the C-terminal carboxylate and peptide NH groups at neutral and high pH; and a seven-membered COH...O = C hydrogen-bonded ring between the C-terminal carboxyl OH and peptide C = O groups at low pH. In the N-terminal alanyl residue, the peptide C = O group is hydrogen bonded to the NH trans to the methine bond. The CH-stretching VCD spectra of L-alanyl-L-alanyl-L-alanine at neutral pH are consistent with two intramolecularly hydrogen-bonded conformations for the central alanyl residue.
Assuntos
Dipeptídeos , Alanina , Dicroísmo Circular , Concentração de Íons de Hidrogênio , Peptídeos , Conformação Proteica , SoluçõesRESUMO
In 1838 a differential equation was developed by Verhulst to explain what is currently termed the S-shaped curve. Reviewed here are his application of the equation to population data and significant later applications by various workers to problems in physics, chemistry, and biology. The usefulness, versatility, and convenience of this integrated equation are illustrated by examples from our own work, including superimposition of data by use of reduced variables.