TY - JOUR A1 - Graf, Philipp A1 - Mantion, Alexandre A1 - Haase, Andrea A1 - Thuenemann, Andreas F. A1 - Masic, Admir A1 - Meier, Wolfgang P. A1 - Luch, Andreas A1 - Taubert, Andreas T1 - Silicification of peptide-coated silver nanoparticles-A biomimetic soft chemistry approach toward chiral hybrid core-shell materials JF - ACS nano N2 - 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. KW - peptide-templated materials KW - silver nanoparticles KW - chiral nanoparticles KW - Ag/peptide@SiO(2) nanostructures KW - core-shell structures Y1 - 2011 U6 - https://doi.org/10.1021/nn102969p SN - 1936-0851 VL - 5 IS - 2 SP - 820 EP - 833 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Haase, Andrea A1 - Rott, Stephanie A1 - Mantion, Alexandre A1 - Graf, Philipp A1 - Plendl, Johanna A1 - Thünemann, Andreas F. A1 - Meier, Wolfgang P. A1 - Taubert, Andreas A1 - Luch, Andreas A1 - Reiser, Georg T1 - Effects of silver nanoparticles on primary mixed neural cell cultures: Uptake, oxidative stress and acute calcium responses JF - Toxicological sciences N2 - In the body, nanoparticles can be systemically distributed and then may affect secondary target organs, such as the central nervous system (CNS). Putative adverse effects on the CNS are rarely investigated to date. Here, we used a mixed primary cell model consisting mainly of neurons and astrocytes and a minor proportion of oligodendrocytes to analyze the effects of well-characterized 20 and 40 nm silver nanoparticles (SNP). Similar gold nanoparticles served as control and proved inert for all endpoints tested. SNP induced a strong size-dependent cytotoxicity. Additionally, in the low concentration range (up to 10 mu g/ml of SNP), the further differentiated cultures were more sensitive to SNP treatment. For detailed studies, we used low/medium dose concentrations (up to 20 mu g/ml) and found strong oxidative stress responses. Reactive oxygen species (ROS) were detected along with the formation of protein carbonyls and the induction of heme oxygenase-1. We observed an acute calcium response, which clearly preceded oxidative stress responses. ROS formation was reduced by antioxidants, whereas the calcium response could not be alleviated by antioxidants. Finally, we looked into the responses of neurons and astrocytes separately. Astrocytes were much more vulnerable to SNP treatment compared with neurons. Consistently, SNP were mainly taken up by astrocytes and not by neurons. Immunofluorescence studies of mixed cell cultures indicated stronger effects on astrocyte morphology. Altogether, we can demonstrate strong effects of SNP associated with calcium dysregulation and ROS formation in primary neural cells, which were detectable already at moderate dosages. KW - silver nanoparticles KW - neurons KW - oxidative stress KW - protein carbonyls KW - calcium Y1 - 2012 U6 - https://doi.org/10.1093/toxsci/kfs003 SN - 1096-6080 VL - 126 IS - 2 SP - 457 EP - 468 PB - Oxford Univ. Press CY - Oxford ER - TY - THES A1 - Heck, Christian T1 - Gold and silver nanolenses self-assembled by DNA origami T1 - Gold- und Silbernanolinsen, selbstassembliert durch DNA-Origami N2 - Nanolenses are linear chains of differently-sized metal nanoparticles, which can theoretically provide extremely high field enhancements. The complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, the technique of DNA origami was used to self-assemble DNA-coated 10 nm, 20 nm, and 60 nm gold or silver nanoparticles into gold or silver nanolenses. Three different geometrical arrangements of gold nanolenses were assembled, and for each of the three, sets of single gold nanolenses were investigated in detail by atomic force microscopy, scanning electron microscopy, dark-field scattering and Raman spectroscopy. The surface-enhanced Raman scattering (SERS) capabilities of the single nanolenses were assessed by labelling the 10 nm gold nanoparticle selectively with dye molecules. The experimental data was complemented by finite-difference time-domain simulations. For those gold nanolenses which showed the strongest field enhancement, SERS signals from the two different internal gaps were compared by selectively placing probe dyes on the 20 nm or 60 nm gold particles. The highest enhancement was found for the gap between the 20 nm and 10 nm nanoparticle, which is indicative of a cascaded field enhancement. The protein streptavidin was labelled with alkyne groups and served as a biological model analyte, bound between the 20 nm and 10 nm particle of silver nanolenses. Thereby, a SERS signal from a single streptavidin could be detected. Background peaks observed in SERS measurements on single silver nanolenses could be attributed to amorphous carbon. It was shown that the amorphous carbon is generated in situ. N2 - Nanolinsen sind Strukturen aus linear angeordneten, unterschiedlich großen metallischen Nanopartikeln. Elektromagnetische Felder können durch sie theoretisch extrem verstärkt werden, aufgrund ihres komplexen Aufbaus sind sie bislang aber wenig erforscht. Im Rahmen dieser Dissertation wurden Nanolinsen mit Hilfe der DNA-Origami-Technik aus DNA-beschichteten 10 nm-, 20 nm- und 60 nm-Gold- oder Silbernanopartikeln hergestellt. Für Goldnanolinsen sind die Partikel dabei in drei unterschiedlichen Geometrien angeordnet worden. Einzelne Goldnanolinsen wurden mittels Rasterkraftmikroskopie, Rasterelektronenmikroskopie, Dunkelfeld- und Ramanspektroskopie untersucht. Um die Raman-Verstärkung quantifizieren zu können, trugen dabei jeweils die 10 nm-Goldpartikel Farbstoffmoleküle in ihrer Beschichtung. Die Interpretation der Messdaten wurde durch numerische Simulationen unterstützt. Nanolinsen zeichnen sich durch eine stufenweise Feldverstärkung aus. Dieser Effekt konnte experimentell bestätigt werden, indem selektiv die 20 nm- oder 60 nm-Partikel von Goldnanolinsen mit Farbstoffen markiert und die resultierenden Raman-Signale verglichen wurden. Ein mit Alkingruppen markiertes Protein ist ortsselektiv in Silbernanolinsen integriert worden. Es war möglich, das für das Alkin charakteristische oberflächenverstärkte Raman-Signal im Spektrum einer einzelnen Nanolinse und damit eines einzelnen Proteins zu beobachten. Bei den Messungen mit Silbernanolinsen sind für amorphe Kohlenstoffspezies charakterstische Hintergrundsignale beobachtet worden. Durch zeitabhängige Messungen konnte gezeigt werden, dass diese Spezies erst in situ gebildet werden. KW - DNA origami KW - gold nanoparticles KW - silver nanoparticles KW - SERS KW - self-assembly KW - plasmonics KW - nanolenses KW - DNA-Origami KW - Goldnanopartikel KW - Silbernanopartikel KW - SERS KW - Selbstassemblierung KW - Plasmonik KW - Nanolinsen Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-409002 ER - TY - JOUR A1 - Heck, Christian A1 - Kanehira, Yuya A1 - Kneipp, Janina A1 - Bald, Ilko T1 - Placement of Single Proteins within the SERS Hot Spots of Self-Assembled Silver Nanolenses JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - This study demonstrates the bottom-up synthesis of silver nanolenses. A robust coating protocol enabled the functionalization of differently sized silver nanoparticles with DNA single strands of orthogonal sequence. Coated particles 10nm, 20nm, and 60nm in diameter were self-assembled by DNA origami scaffolds to form silver nanolenses. Single molecules of the protein streptavidin were selectively placed in the gap of highest electric field enhancement. Streptavidin labelled with alkyne groups served as model analyte in surface-enhanced Raman scattering (SERS) experiments. By correlated Raman mapping and atomic force microscopy, SERS signals of the alkyne labels of a single streptavidin molecule, from a single silver nanolens, were detected. The discrete, self-similar aggregates of solid silver nanoparticles are promising for plasmonic applications. KW - DNA origami KW - protein analysis KW - SERS KW - silver nanoparticles KW - streptavidin Y1 - 2018 U6 - https://doi.org/10.1002/anie.201801748 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 25 SP - 7444 EP - 7447 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Lutze, Jana A1 - Bañares, Miguel A. A1 - Pita, Marcos A1 - Haase, Andrea A1 - Luch, Andreas A1 - Taubert, Andreas T1 - alpha-((4-Cyanobenzoyl)oxy)-omega-methyl poly(ethylene glycol) BT - a new stabilizer for silver nanoparticles JF - Beilstein journal of nanotechnology N2 - The article describes the synthesis and properties of alpha-((4-cyanobenzoyl)oxy)-omega-methyl poly(ethylene glycol), the first poly(ethylene glycol) stabilizer for metal nanoparticles that is based on a cyano rather than a thiol or thiolate anchor group. The silver particles used to evaluate the effectiveness of the new stabilizer typically have a bimodal size distribution with hydrodynamic diameters of ca. 13 and ca. 79 nm. Polymer stability was evaluated as a function of the pH value both for the free stabilizer and for the polymers bound to the surface of the silver nanoparticles using H-1 NMR spectroscopy and zeta potential measurements. The polymer shows a high stability between pH 3 and 9. At pH 12 and higher the polymer coating is degraded over time suggesting that alpha-((4-cyanobenzoyl) oxy)-omega-methyl poly(ethylene glycol) is a good stabilizer for metal nanoparticles in aqueous media unless very high pH conditions are present in the system. The study thus demonstrates that cyano groups can be viable alternatives to the more conventional thiol/thiolate anchors. KW - cyano anchor group KW - poly(ethylene glycol) KW - polymer coating KW - silver nanoparticles Y1 - 2017 U6 - https://doi.org/10.3762/bjnano.8.67 SN - 2190-4286 VL - 8 SP - 627 EP - 635 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER - TY - JOUR A1 - Tentschert, J. A1 - Draude, F. A1 - Jungnickel, H. A1 - Haase, A. A1 - Mantion, Alexandre A1 - Galla, S. A1 - Thuenemann, Andreas F. A1 - Taubert, Andreas A1 - Luch, A. A1 - Arlinghaus, H. F. T1 - TOF-SIMS analysis of cell membrane changes in functional impaired human macrophages upon nanosilver treatment JF - Surface and interface analysis : an international journal devoted to the development and application of techniques for the analysis surfaces, interfaces and thin films N2 - 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. KW - silver nanoparticles KW - lipidomics KW - N-acetyl cysteine KW - phagocytosis KW - oxidative stress Y1 - 2013 U6 - https://doi.org/10.1002/sia.5155 SN - 0142-2421 VL - 45 IS - 1 SP - 483 EP - 485 PB - Wiley-Blackwell CY - Hoboken ER -