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Photomodulation of the Redox and Folding Adjuvant Properties of Bis(cysteinyl) Peptides
Author(s) -
Cabrele Chiara,
CattaniScholz Anna,
Renner Christian,
Behrendt Raymond,
Oesterhelt Dieter,
Moroder Luis
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200207)2002:13<2144::aid-ejoc2144>3.0.co;2-i
Subject(s) - chemistry , azobenzene , moiety , oxidative folding , stereochemistry , peptide , thioredoxin reductase , isomerization , folding (dsp implementation) , thiol , thioredoxin , rnase p , cyclic peptide , redox , combinatorial chemistry , disulfide bond , protein disulfide isomerase , biochemistry , enzyme , organic chemistry , molecule , catalysis , rna , electrical engineering , gene , engineering
Abstract The octapeptide [134−141] related to the active‐site fragment of thioredoxin reductase, in which three residues outside the characteristic Cys‐Xaa‐Yaa‐Cys motif of thiol/disulfide oxidoreductases were replaced by lysines, was head‐to‐tail‐cyclized by using the suitably functionalized (4‐aminomethyl)phenylazobenzoic acid (AMPB). The resulting monocyclic and disulfide‐bridged bicyclic compounds underwent light‐induced cis / trans isomerization in a fully reversible manner, with well‐defined conformational transitions as a result of the strong differences in the molecular geometries of the trans ‐ and cis ‐azobenzene units. Correspondingly, the trans and cis forms of the cyclic bis(cysteinyl)‐AMPB peptide were characterized by significantly differentiated redox potentials, which were exploited to catalyze the oxidative refolding of reduced RNase A with distinct efficiencies. The experimental results showed that the incorporation of the azobenzene moiety into conformationally restricted bis(cysteinyl) peptide systems provided folding adjuvants that photocontrolled the rates of oxidative protein folding. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)