Formation of Silver Nanoparticles by Electron Transfer in Peptides and c-Cytochromes.

The reduction of Ag+ ions to Ag0 atoms is a highly endergonic reaction step, only the aggregation to Agn clusters leads to an exergonic process. These elementary chemical reactions play a decisive role if Ag nanoparticles (AgNPs) are generated by electron transfer (ET) reactions to Ag+ ions. We studied the formation of AgNPs in peptides by photoinduced ET, and in c-cytochromes by ET from their Fe2+ /hemes. Our earlier photoinduced experiments in peptides had demonstrated that histidine prevents AgNP formation. We have now observed that AgNPs can be easily synthesized with less-efficient Ag+ -binding amino acids, and the rate increases in the order lysine

Electron transfer in peptides: on the formation of silver nanoparticles.

Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag(+) ions bound by peptides with histidine as the Ag(+)-binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time-resolved UV/Vis spectra which exhibit an isosbestic point.

The search for relay stations. Long-distance electron transfer in peptides.

Nature uses peptide aggregates as soft materials for electron transfer over long distances. These reactions occur in a multistep hopping reaction with various functional groups as relay stations that are located in the side chain and in the backbone of the peptides.