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Organisationseinheit der BAM
AbstractWe report on gold clusters with around 62 gold atoms and a diameter of 1.15±0.10 nm. Dispersions of the clusters are long‐term stable for two years at ambient conditions. The synthesis was performed by mixing tetrachloroauric acid (HAuCl4 ⋅ 3 H2O) with the ionic liquid 1‐ethyl‐3‐methylimidazolium dicyanamide ([Emim][DCA]) at temperatures of 20 to 80 °C. Characterization was performed with small‐angle X‐ray scattering (SAXS), UV‐Vis spectroscopy, and MALDI‐TOF mass spectrometry. A three‐stage model is proposed for the formation of the clusters, in which cluster growth from gold nuclei takes place according to the Lifshitz‐Slyozov‐Wagner (LSW) model followed by oriented attachment to form colloidal stable clusters.
Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N′,N′-tetramethyl-N,N′-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers.
Silica and silver nanoparticles are relevant materials for new applications in optics, medicine, and analytical chemistry. We have previously reported the synthesis of pH responsive, peptide-templated, chiral silver nanoparticles. The current report shows that peptide-stabilized nanoparticles can easily be coated with a silica shell by exploiting the ability of the peptide coating to hydrolyze silica precursors such as TEOS or TMOS. The resulting silica layer protects the nanoparticles from chemical etching, allows their inclusion in other materials, and renders them biocompatible. Using electron and atomic force microscopy, we show that the silica shell thickness and the particle aggregation can be controlled simply by the reaction time. Small-angle X ray scattering confirms the Ag/peptide@silica core–shell structure. UV–vis and circular dichroism spectroscopy prove the conservation of the silver nanoparticle chirality upon silicification. Biological tests show that the biocompatibility in simple bacterial systems is significantly improved once a silica layer is deposited on the silver particles.
Ionic liquids (ILs) have attracted tremendous interest in the recent past for their potential in many chemical fields. The current report explores the effects of a set of ILs based on the 1-ethyl-3-methyl-imidazolium cation and different anions on the formation of gold nanoparticles. X-Ray diffraction finds face-centered cubic gold in all cases, but transmission electron microscopy (TEM) shows that there are distinct differences in particle formation and stabilization with the ethyl sulfate (ES), trifluoromethanesulfonate (TfO) and methanesulfonate (MS) anions. With the MS anion, nanoparticles with diameters between 5 and 7 nm form, which increasingly aggregate at higher reaction temperatures. With TfO, also small 5 to 7 nm particles form, but only at low temperatures. Above ca. 160 °C, large, ill-defined and aggregated particles form. With ES, polydisperse samples form at all temperatures except 160 °C. In this case the nanoparticles appear often surrounded by an IL film, which appears to stabilize individual, ca. 15 to 20 nm particles. Dynamic light scattering and UV/Vis spectroscopy further show that in suspension the particles are, much like seen in the TEM, more strongly aggregated with higher reaction temperatures. In summary, the results suggest that there are very specific IL-gold interactions that are responsible for the formation of gold particles with an IL-specific shape, size, and aggregation behavior.
Nanosilver is increasingly used in optics, medicine and analytical chemistry. We recently reported on the synthesis and properties of novel peptide-coated chiral nanosilver [1] using a small hexapeptide based on the amino acids CKK. In a continuation of our previous work, we use the peptides to catalyse TEOS hydrolysis in order to form a dense silica layer shell around a single nanoparticle, preventing chemical etching, allowing their inclusion in other inorganics, and making them biocompatible. Because of mild reaction conditions, the peptide integrity is ensured, as the chiral information which is contained in the nanoparticle. Moreover, these novel core-shell structures remain well-dispersed and are biocompatible. The possibility of further processing (creation of metamaterials etc.) is also in the focus of our interest.
Silver nanoparticles (SNP) are the subject of worldwide commercialization because of their antimicrobial effects. Yet only little data on their mode of action exist. Further, only few techniques allow for visualization and quantification of unlabeled nanoparticles inside cells. To study SNP of different sizes and coatings within human macrophages, we introduce a novel laser postionization secondary neutral mass spectrometry (Laser-SNMS) approach and prove this method superior to the widely applied confocal Raman and transmission electron microscopy. With time-of-flight secondary ion mass spectrometry (TOF-SIMS) we further demonstrate characteristic fingerprints in the lipid pattern of the cellular membrane indicative of oxidative stress and membrane fluidity changes. Increases of protein carbonyl and heme oxygenase-1 levels in treated cells confirm the presence of oxidative stress biochemically. Intriguingly, affected phagocytosis reveals as highly sensitive end point of SNP-mediated adversity in macrophages. The cellular responses monitored are hierarchically linked, but follow individual kinetics and are partially reversible.
Silver nanoparticles (SNP) are among the most commercialized nanoparticles. Here, we show that peptide-coated SNP cause functional impairment of human macrophages. A dose-dependent inhibition of phagocytosis is observed after nanoparticle treatment, and pretreatment of cells with N-acetyl cysteine (NAC) can counteract the phagocytosis disturbances caused by SNP.
Using the surface-sensitive mode of time-of-flight secondary ion mass spectrometry, in combination with multivariate statistical methods, we studied the composition of cell membranes in human macrophages upon exposure to SNP with and without NAC preconditioning. This method revealed characteristic changes in the lipid pattern of the cellular membrane outer leaflet in those cells challenged by SNP. Statistical analyses resulted in 19 characteristic ions, which can be used to distinguish between NAC pretreated and untreated macrophages. The present study discusses the assignments of surface cell membrane phospholipids for the identified ions and the resulting changes in the phospholipid pattern of treated cells. We conclude that the adverse effects in human macrophages caused by SNP can be partially reversed through NAC administration. Some alterations, however, remained.
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.
Dispersions of Fe3C nanoparticles in several ionic liquids (ILs) have been investigated. The ILs are based on 1-ethyl-3-methylimidazolium [Emim] and 1-butyl-3-methylimidazolium [Bmim] cations. Anions are ethylsulfate [ES], methanesulfonate [MS], trifluoromethylsulfonate (triflate) [TfO], tetrafluoroborate [BF4], dicyanamide [N(CN)2], and thiocyanate [SCN]. Among the ILs studied, [Emim][SCN] and [Emim][N(CN)2] stand out because only in these ILs have stable and transparent nanoparticle dispersions been obtained. All other ILs lead to blackish, slightly turbid dispersions or to completely nontransparent suspensions, which often contain undispersed sediment. UV/vis spectroscopy, transmission electron microscopy, and X-ray scattering suggest that the reason for the stabilization of the Fe3C nanoparticles in [Emim][SCN] is the leaching of traces of iron from the particles (without affecting the crystal structure of the Fe3C particles). The resulting particle surface is thus carbon-rich, which presumably favors the stabilization of the particles. A similar explanation can be postulated for [Emim][N(CN)2], with the dicyanamide anion also being a good ligand for iron.
Silver nanoparticles (SNP) are among the most commercialized nanoparticles worldwide. They can be found in many diverse products, mostly because of their antibacterial properties. Despite its widespread use only little data on possible adverse health effects exist. It is difficult to compare biological data from different studies due to the great variety in sizes, coatings or shapes of the particles. Here, we applied a novel synthesis approach to obtain SNP, which are covalently stabilized by a small peptide. This enables a tight control of both size and shape. We applied these SNP in two different sizes of 20 or 40 nm (Ag20Pep and Ag40Pep) and analyzed responses of THP-1-derived human macrophages. Similar gold nanoparticles with the same coating (Au20Pep) were used for comparison and found to be non-toxic. We assessed the cytotoxicity of particles and confirmed their cellular uptake via transmission electron microscopy and confocal Raman microscopy. Importantly a majority of the SNP could be detected as individual particles spread throughout the cells. Furthermore we studied several types of oxidative stress related responses such as induction of heme oxygenase I or formation of protein carbonyls. In summary, our data demonstrate that even low doses of SNP exerted adverse effects in human macrophages.