Reengineering a Type II b -Turn as a Potential Helix Nucleator-NMR Characterization of Boc-Ala-Val-Pro-(D) Asp-Leu-Leu-NHMe

E.B. Raju 1 , M. Dhanasekaran 1 , S. Durani 1 , S. Srivastava 2,*

1. Department o f Chemistry & Biotechnology Centre, Indian Institute of Technology, Bombay, India 400 076 (India)
2. National Facility for High Field NMR, Tata Institute of Fundamental Research, Homi Bhabha Road, Navy Nagar, Mumbai -400005 (India)

Manuscript received: May 3, 1999; revised: July 29, 1999.

Accepted for publication: September 10, 1999.

Abstract

A stereochemically constrained type II b -turn is reengineered over two steps into a potential helix nucleator. NMR studies in DMSO establish that the hexapeptide Boc-Ala1-Val2-Pro3-(D)Asp4-Leu5-Leu6-NHMe is a type II b -turn at Pro3-(D)Asp4 with a conformation nucleating H-bond between Asp4 carboxylate and Leu6 NH, to which is attributable a type I/III b -turn at Leu5-Leu6- NHMe potentially capable of serving as a helix template.

KEYWORDS: Type II b -turn, D-amino acid, Peptide, NMR, Helix.

Abbreviations

NMM-N-Methyl Morpholine, IBCF-Isobutyl chloroformate, DCC - Dicyclohexyl carbodiimide, HOBt - Hydroxy benzotriazole, TFA-Trifluoroacetic Acid, COSY-Correlation spectroscopy, TOCSY-Total Correlation spectroscopy, ROESY-Rotating frame nuclear Overhauser enhancement spectroscopy, NOE- Nuclear Overhauser effect.

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