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Simple tripeptides are scaffolds for the synthesis and further assembly of peptide/silver nanoparticle composites. Herein, we further explore peptide-controlled silver nanoparticle assembly processes. Silver nanoparticles with a pH-responsive peptide coating have been synthesized by using a one-step precipitation/coating route. The nature of the peptide/silver interaction and the effect of the peptide on the formation of the silver particles have been studied via UV/Vis, X-ray photoelectron, and surface-enhanced Raman spectroscopies as well as through electron microscopy, small angle X-ray scattering and powder X-ray diffraction with Rietveld refinement. The particles reversibly form aggregates of different sizes in aqueous solution. The state of aggregation can be controlled by the solution pH value. At low pH values, individual particles are present. At neutral pH values, small clusters form and at high pH values, large precipitates are observed.
Silver nanoparticles (SNPs) are among the most commercialized nanoparticles because of their antibacterial effects. Besides being employed, e.g. as a coating material for sterile surfaces in household articles and appliances, the particles are also used in a broad range of medical applications. Their antibacterial properties make SNPs especially useful for wound disinfection or as a coating material for prostheses and surgical instruments. Because of their optical characteristics, the particles are of increasing interest in biodetection as well. Despite the widespread use of SNPs, there is little knowledge of their toxicity. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and laser post-ionization secondary neutral mass spectrometry (Laser-SNMS) were used to investigate the effects of SNPs on human macrophages derived from THP-1 cells in vitro. For this purpose, macrophages were exposed to SNPs. The SNP concentration ranges were chosen with regard to functional impairments of the macrophages. To optimize the analysis of the macrophages, a special silicon wafer sandwich preparation technique was employed; ToF-SIMS was employed to characterize fragments originating from macrophage cell membranes. With the use of this optimized sample preparation method, the SNP-exposed macrophages were analyzed with ToF-SIMS and with Laser-SNMS. With Laser-SNMS, the three-dimensional distribution of SNPs in cells could be readily detected with very high efficiency, sensitivity, and submicron lateral resolution. We found an accumulation of SNPs directly beneath the cell membrane in a nanoparticular state as well as agglomerations of SNPs inside the cells.
A broad range of new properties is emerging from supramolecular aggregates as they pass beyond the limitations of simple molecules. Self-assembled structures of purely peptidic amphiphiles may exploit such properties to produce biocompatible, smart materials for drug administration. In aqueous media, the solid-phase derived amphiphilic undecapeptide described herein (Ac-X3-gT) forms self-assembled particles of spherical shape with diameters between 200 and 1500 nm, termed 'peptide beads'. The beads result from hierarchical organization of micellar-like structures, a fact determined by a combination of investigations carried out by electron and atomic force microscopy (AFM), static and dynamic light scattering, and small-angle X-ray scattering. These highly ordered structures agree with the concept of multicompartmentization and represent the first example of supramicellar assemblies based purely on peptides. New structural insights, as presented here, allow a better understanding of the beads' capacity to embed hydrophobic and hydrophilic payloads and therefore provide new perspectives for drug delivery applications that may result from this new class of material.