Armin Hoell

Photoluminescence of atomic gold and silver particles in soda-lime silicate glasses

We report the chemistry and photophysics of atomic gold and silver particles in inorganic glasses. By synchrotron irradiation of gold-doped soda-lime silicate glasses we could create and identify unambiguously the gold dimer as a stable and bright luminescing particle embedded in the glassy matrix. The gold dimer spectra coincide perfectly with rare gas matrix spectra of Au(2). The glass matrix is, however, stable for years, and is hence perfectly suited for various applications. If the irradiated gold-doped sample is annealed at 550 degrees C a bright green luminescence can be recognized. Intense 337 nm excitation induces a decrease of the green luminescence and the reappearance of the 753 nm Au(2) emission, indicating a strong interrelationship between both luminescence centers. Time-dependent density functional theory (TD-DFT) calculations indicate that the green luminescence can be assigned to noble metal dimers bound to silanolate centers. These complexes are recognized as the first stages in the further cluster growth process, which has been investigated with small-angle x-ray scattering (SAXS). In silver-doped glasses, Ag(0) atoms can be identified with electron paramagnetic resonance (EPR) spectroscopy after synchrotron activation. Annealing at 300 degrees C decreases the concentration of Ag(1), but induces an intense white light emission with 337 nm excitation. The white luminescence can be decomposed into bands that are attributed to small silver clusters such as Ag(2), Ag(3) and Ag(4), and an additional band matching the green emission of gold-doped glasses.

Mechanical Stability and Fibrinolytic Resistance of Clots Containing Fibrin, DNA, and Histones

Background: Neutrophil extracellular traps (NETs) composed of DNA and proteins form a scaffold in thrombi, supplementing the fibrin matrix. Results: DNA and histones modify the structure of fibrin and render it resistant to mechanical and enzymatic destruction. Conclusion: NET components are essential factors in thrombus stability. Significance: Therapeutic strategies could be optimized to enhance fibrinolysis in clots containing DNA and histones. Neutrophil extracellular traps are networks of DNA and associated proteins produced by nucleosome release from activated neutrophils in response to infection stimuli and have recently been identified as key mediators between innate immunity, inflammation, and hemostasis. The interaction of DNA and histones with a number of hemostatic factors has been shown to promote clotting and is associated with increased thrombosis, but little is known about the effects of DNA and histones on the regulation of fibrin stability and fibrinolysis. Here we demonstrate that the addition of histone-DNA complexes to fibrin results in thicker fibers (increase in median diameter from 84 to 123 nm according to scanning electron microscopy data) accompanied by improved stability and rigidity (the critical shear stress causing loss of fibrin viscosity increases from 150 to 376 Pa whereas the storage modulus of the gel increases from 62 to 82 pascals according to oscillation rheometric data). The effects of DNA and histones alone are subtle and suggest that histones affect clot structure whereas DNA changes the way clots are lysed. The combination of histones + DNA significantly prolongs clot lysis. Isothermal titration and confocal microscopy studies suggest that histones and DNA bind large fibrin degradation products with 191 and 136 nm dissociation constants, respectively, interactions that inhibit clot lysis. Heparin, which is known to interfere with the formation of neutrophil extracellular traps, appears to prolong lysis time at a concentration favoring ternary histone-DNA-heparin complex formation, and DNase effectively promotes clot lysis in combination with tissue plasminogen activator.

Silver Ion Incorporation and Nanoparticle Formation Inside the Cavity of Pyrococcus Furiosus Ferritin: Structural and Size-Distribution Analyses.

Highly symmetrical protein cage architectures from three different iron storage proteins, heavy and light human ferritin chains (HuHFt and HuLFt) and ferritin from the hyperthemophilic bacterium Pyrococcus furiosus (PfFt), have been used as models for understanding the molecular basis of silver ion deposition and metal core formation inside the protein cavity. Biomineralization using protein cavities is an important issue for the fabrication of biometamaterials under mild synthetic conditions. Silver nanoparticles (AgNPs) were produced with high yields within PfFt but not within HuHFt and HuLFt. To explain the molecular basis of silver incorporation, the X-ray crystal structure of Ag-containing PfFt has been solved. This is the first structure of a silver containing ferritin reported to date, and it revealed the presence of specific binding and nucleation sites of Ag(I) that are not conserved in other ferritin templates. The AgNP encapsulated by PfFt were further characterized by the combined use of different physical-chemical techniques. These showed that the AgNPs are endowed with a narrow size distribution (2.1 +/- 0.4 nm), high stability in water solution at millimolar concentration, and high thermal stability. These properties make the AgNP obtained within PftFt exploitable for a range of applications, in fields as diverse as catalysis in water, preparation of metamaterials, and in vivo diagnosis and antibacterial or tumor therapy.

In situ study of atomic structure transformations of Pt-Ni nanoparticle catalysts during electrochemical potential cycling.

When exposed to corrosive anodic electrochemical environments, Pt alloy nanoparticles (NPs) undergo selective dissolution of the less noble component, resulting in catalytically active bimetallic Pt-rich core-shell structures. Structural evolution of PtNi6 and PtNi3 NP catalysts during their electrochemical activation and catalysis was studied by in situ anomalous small-angle X-ray scattering to obtain insight in element-specific particle size evolution and time-resolved insight in the intraparticle structure evolution. Ex situ high-energy X-ray diffraction coupled with pair distribution function analysis was employed to obtain detailed information on the atomic-scale ordering, particle phases, structural coherence lengths, and particle segregation. Our studies reveal a spontaneous electrochemically induced formation of PtNi particles of ordered Au3Cu-type alloy structures from disordered alloy phases (solid solutions) concomitant with surface Ni dissolution, which is coupled to spontaneous residual Ni metal segregation during the activation of PtNi6. Pt-enriched core-shell structures were not formed using the studied Ni-rich nanoparticle precursors. In contrast, disordered PtNi3 alloy nanoparticles lose Ni more rapidly, forming Pt-enriched core-shell structures with superior catalytic activity. Our X-ray scattering results are confirmed by STEM/EELS results on similar nanoparticles.

Nonaqueous Microemulsions Based on N,N′-Alkylimidazolium Alkylsulfate Ionic Liquids

The ternary system composed of the ionic liquid surfactant (IL-S) 1-butyl-3-methylimidazolium dodecylsulfate ([Bmim][DodSO4]), the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]), and toluene has been investigated. Three major mechanisms guiding the structure of the isotropic phase were identified by means of conductometric experiments, which have been correlated to the presence of oil-in-IL, bicontinuous, and IL-in-oil microemulsions. IL-S forms micelles in toluene, which swell by adding RTIL as to be shown by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) experiments. Therefore, it is possible to form water-free IL-in-oil reverse microemulsions ≤10 nm in size as a new type of nanoreactor.

Small-angle neutron and X-ray scattering of dispersions of oleic-acid-coated magnetic iron particles.

This paper describes the characterization of dispersions of oleic-acid-coated magnetic iron particles by small-angle neutron and X-ray scattering (SANS and SAXS). Both oxidized and non-oxidized dilute samples were studied by SANS at different contrasts. The non-oxidized samples are found to consist of noninteracting superparamagnetic single dipolar particles, with a lognormal distribution of iron cores, surrounded by a surfactant shell, which is partially penetrated by solvent. This model is supported by SAXS measurements on the same dispersion. Small iron particles are expected to oxidize upon exposure to air. SANS was used to study the effect of this oxidation, both on single particles, as well as on interparticle interactions. It is found that on exposure to air, a nonmagnetic oxide layer is formed around the iron cores, which causes an increase of particle size. In addition, particles are found to aggregate upon oxidation, presumably because the surfactant density on the particle surfaces is decreased.

A closer look at the structure of sterically stabilized liposomes: a small-angle X-ray scattering study.

The evaluation of the radial electron density profile of a drug containing a sterically stabilized liposomal system is described. Using synchrotron small-angle X-ray scattering, we were able to characterize the hydrophilic shell of the polyethylene glycol chains. Using a Gaussian model for describing the electron density profile along the normal of the bilayer, we got an asymmetric distribution of PEGylated lipids in accordance with theoretical considerations. Moreover, we used anomalous X-ray scattering to study the localization of a hydrophobic drug (a kinase inhibitor), which revealed that these molecules are mainly located in the hydrocarbon chain region of the phospholipid bilayer.

Deep Eutectic Solvents for the Self-Assembly of Gold Nanoparticles: A SAXS, UV–Vis, and TEM Investigation

In this work, we report the formation and growth mechanisms of gold nanoparticles (AuNPs) in eco-friendly deep eutectic solvents (DES; choline chloride and urea). AuNPs are synthesized on the DES surface via a low-energy sputter deposition method. Detailed small angle X-ray scattering (SAXS), UV-Vis, and cryogenic transmission electron microscopy (cryo-TEM) investigations show the formation of AuNPs of 5 nm diameter. Data analysis reveals that for a prolonged gold-sputtering time there is no change in the size of the particles. Only the concentration of AuNPs increases linearly in time. More surprisingly, the self-assembly of AuNPs into a first and second shell ordered system is observed directly by in situ SAXS for prolonged gold-sputtering times. The self-assembly mechanism is explained by the templating nature of DES combined with the equilibrium between specific physical interaction forces between the AuNPs. A disulfide-based stabilizer, bis((2-mercaptoethyl)trimethylammonium) disulfide dichloride, was applied to suppress the self-assembly. Moreover, the stabilizer even reverses the self-assembled or agglomerated AuNPs back to stable 5 nm individual particles as directly evidenced by UV-Vis. The template behavior of DES is compared to that of nontemplating solvent castor oil. Our results will also pave the way to understand and control the self-assembly of metallic and bimetallic nanoparticles.

ASAXS study of CaF2 nanoparticles embedded in a silicate glass matrix

The formation and growth of nanosized CaF2 crystallites by heat treatment of an oxyfluoride glass of composition 7.65Na2O–7.69K2O–10.58CaO–12.5CaF2–5.77Al2O3–55.8SiO2 (wt%) was investigated using anomalous small-angle X-ray scattering (ASAXS). A recently developed vacuum version of the hybrid pixel detector Pilatus 1M was used for the ASAXS measurements below the Ca K-edge of 4038 eV down to 3800 eV. ASAXS investigation allows the determination of structural parameters such as size and size distribution of nanoparticles and characterizes the spatial distribution of the resonant element, Ca. The method reveals quantitatively that the growing CaF2 crystallites are surrounded by a shell of lower electron density. This depletion shell of growing thickness hinders and finally limits the growth of CaF2 crystallites. Moreover, in samples that were annealed for 10 h and more, additional very small heterogeneities (1.6 nm diameter) were found.

Experimental evidence of a diffusion barrier around BaF2 nanocrystals in a silicate glass system by ASAXS

Nanocrystals of BaF2 precipitate during controlled annealing of silicate glasses composed of SiO2, Al2O3, K2O, Na2O, BaF2 and BaO. Structural characteristics such as size, shape, volume fraction and size distribution of nanoparticles in the glass matrix were studied by anomalous small angle x-ray scattering (ASAXS). Fitted ASAXS curves near the Ba absorption edge reveal the formation of a core-shell structure. Furthermore, ASAXS results allowed to determine quantitatively the composition of the nanocrystals, the surrounding region (shell) and the matrix. The evaluated composition gives evidence for an enrichment of Si atoms in a shell, that surrounds the particles and acts as a diffusion barrier. Resonant curve analysis reveals the quantitative information of the Ba atoms used in the formation of BaF2 nanoparticles.