Metallkomplexe mariner Peptidmetaboliten: ein neuartiger Ag₄‐Cluster

Abstract

Stark kooperativ und selektiv gebunden werden Silber(I)‐Ionen von dem aus Lissoclinum gewonnenen Peptid Westiellamid. Der Komplex enthält einen einzigartigen [Ag4]4‐Cluster, der zwischen zwei neutrale, makrocyclische Liganden eingeschoben ist (Bild rechts). Die Bedeutung der Metallbindung für die biologische Aktivität wird noch untersucht.

Ribosomally synthesized and post-translationally modified peptide natural products: overview and recommendations for a universal nomenclature

“…185,207 Notably, several compounds exhibit selective toxicity to certain human cancer cell lines, 207,208 some potently block the human multidrug efflux pump, P-glycoprotein, 209,210 and many cyanobactins are known for their ability to bind transition metals. 207,211,212 …”

Copper(II) Coordination Chemistry of Westiellamide and Its Imidazole, Oxazole, and Thiazole Analogues

“…Systematic metal-ion-binding studies with westiellamide have revealed an affinity for silver(I) involving the formation of a cluster with four silver(I) ions sandwiched by two H 3 L wa macrocycles. [1,36] , and H 3 L 3 are discussed on the basis of spectroscopic data (ESI-MS, UV/Vis/NIR, EPR), spectra simulations, spectrophotometric and polarimetric titrations, and DFT-based model calculations. These complexes are notoriously difficult to isolate as pure materials and they are difficult to crystallize.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The geometric arrangement of the functional groups and the size of the macrocycles suggest that their ) rings instead of oxazoline, is reported. As in the larger patellamide rings, the N heterocycle -N peptide -N heterocycle binding site is highly preorganized for copper(II) coordination.…”

Insights into the Electronic Structure of CuIIBound to an Imidazole Analogue of Westiellamide

“…In addition to the interaction of H 3 L wa with Ag + , Wipf et al also observed weak interactions between westiellamide and other metal ions such as Na + , Cu + , Fe 2+ , Fe 3+ , Hg 2+ , Au 2+ , and Zn 2+ . 32 Investigations of the interaction of Cu II with H 3 L wa and a series of synthetic analogues H 3 L 1−3 (Figure 1) revealed that after addition of base all cyclic pseudo hexapeptides readily form stable mono-and dinuclear Cu II complexes. 22 In the absence of base, Cu II forms a 2:1 (H 3 L 2 /Cu II ) complex in which Cu II is coordinated to the outside of the macrocycle through the carbonyl oxygen atoms of the peptide bonds, 22 in a similar manner to the central Ag + ion in the unusual [Ag 4 -(H 3 L wa ) 2 ] complex reported by Wipf et al 32 Previous investigations of the Cu II coordination chemistry of the cyclic pseudo hexapeptides H 3 L 1−3 and models for the natural cyclic pseudo peptide westiellamide H 3 L wa revealed interesting differences in their geometric and electronic structures.…”