Universal simulation of absorption effects for X-ray diffraction in reflection geometry.

Analytical calculations of absorption corrections for X-ray powder diffraction experiments on non-ideal samples with surface roughness, porosity or absorption contrasts from multiple phases require complex mathematical models to represent their material distribution. In a computational approach to this problem, a practicable ray-tracing algorithm is formulated which is capable of simulating angle-dependent absorption corrections in reflection geometry for any given rasterized sample model. Single or multiphase systems with arbitrary surface roughness, porosity and spatial distribution of the phases in any combination can be modeled on a voxel grid by assigning respective values to each voxel. The absorption corrections are calculated by tracing the attenuation of X-rays along their individual paths via a modified shear-warp algorithm. The algorithm is presented in detail and the results of simulated absorption corrections on samples with various surface modulations are discussed in the context of published experimental results.

Isolated Rh atoms in dehydrogenation catalysis.

Isolated active sites have great potential to be highly efficient and stable in heterogeneous catalysis, while enabling low costs due to the low transition metal content. Herein, we present results on the synthesis, first catalytic trials, and characterization of the Ga9Rh2 phase and the hitherto not-studied Ga3Rh phase. We used XRD and TEM for structural characterization, and with XPS, EDX we accessed the chemical composition and electronic structure of the intermetallic compounds. In combination with catalytic tests of these phases in the challenging propane dehydrogenation and by DFT calculations, we obtain a comprehensive picture of these novel catalyst materials. Their specific crystallographic structure leads to isolated Rhodium sites, which is proposed to be the decisive factor for the catalytic properties of the systems.

NOBF4-Functionalized Au-Fe3O4 Nanoheterodimers for Radiation Therapy: Synergy Effect Due to Simultaneous Reactive Oxygen and Nitrogen Species Formation.

Snowman-shaped Au-Fe3O4 nanoheterodimers were synthesized by thermal decomposition of iron oleate on presynthesized Au nanoparticles. Subsequently performed ligand exchange with nitrosyl tetrafluoroborate provided water solubility and enabled X-ray-induced NO release. These Au-Fe3O4 nanoheterodimers combine high- Z material with catalytically active Fe3O4 surfaces and, moreover, plasmonic properties with superparamagnetic performance. We could establish synergetic interactions between X-radiation and both the Au and Fe3O4 surfaces, which resulted in the simultaneous production of the nitric oxide radical at the Fe3O4 surface and the superoxide radical at the Au surface. The surface-confined reaction between these radicals generated peroxynitrite. This highly reactive species may cause nitration of mitochondrial proteins and lipid peroxidation and induce DNA strand breaks. Therefore, high concentrations of peroxynitrite are expected to give rise to severe cellular energetic derangements and thereupon entail rapid cell death. As providing a common platform for X-ray-induced formation of the highly reactive radical nitric oxide, superoxide, and peroxynitrite, nitrosyl tetrafluoroborate functionalized Au-Fe3O4 nanosnowmen were shown to exhibit excellent performance as X-ray-enhancing agents in radiation therapy.

Enhanced In Vitro Biocompatibility and Water Dispersibility of Magnetite and Cobalt Ferrite Nanoparticles Employed as ROS Formation Enhancer in Radiation Cancer Therapy.

Efficient magnetic reactive oxygen species (ROS) formation enhancing agents after X-ray treatment are realized by functionalizing superparamagnetic magnetite (Fe3 O4 ) and Co-ferrite (CoFe2 O4 ) nanoparticles with self-assembled monolayers (SAMs). The Fe3 O4 and CoFe2 O4 nanoparticles are synthesized using Massart's coprecipitation technique. Successful surface modification with the SAM forming compounds 1-methyl-3-(dodecylphosphonic acid) imidazolium bromide, or (2-{2-[2-hydroxy-ethoxy]-ethoxy}-ethyl phosphonic acid provides biocompatibility and long-term stability of the Fe3 O4 and CoFe2 O4 nanoparticles in cell media. The SAM-stabilized ferrite nanoparticles are characterized with dynamic light scattering, X-ray powder diffraction, a superconducting quantum interference device, Fourier transform infrared attenuated total reflectance spectroscopy, zeta potential measurements, and thermogravimetric analysis. The impact of the SAM-stabilized nanoparticles on the viability of the MCF-7 cells and healthy human umbilical vein endothelial cells (HUVECs) is assessed using the neutral red assay. Under X-ray exposure with a single dosage of 1 Gy the intracellular SAM stabilized Fe3 O4 and CoFe2 O4 nanoparticles are observed to increase the level of ROS in MCF-7 breast cancer cells but not in healthy HUVECs. The drastic ROS enhancement is associated with very low dose modifying factors for a survival fraction of 50%. This significant ROS enhancement effect by SAM-stabilized Fe3 O4 and CoFe2 O4 nanoparticles constitutes their excellent applicability in radiation therapy.

Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals.

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH2)2PbX3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

Ligand-assisted thickness tailoring of highly luminescent colloidal CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets.

Quantum size-confined CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets with remarkably high photoluminescence quantum yield (up to 90%) were synthesized by ligand-assisted re-precipitation. Thickness-tunability was realized by varying the oleylamine and oleic acid ligand ratio. This method allows tailoring the nanoplatelet thickness by adjusting the number of unit cell monolayers. Broadly tunable emission wavelengths (450-730 nm) are achieved via the pronounced quantum size effect without anion-halide mixing.

Low-Temperature Solution-Processed Kesterite Solar Cell Based on in Situ Deposition of Ultrathin Absorber Layer.

The production of high-performance, solution-processed kesterite Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) solar cells typically relies on high-temperature crystallization processes in chalcogen-containing atmosphere and often on the use of environmentally harmful solvents, which could hinder the widespread adoption of this technology. We report a method for processing selenium free Cu2ZnSnS4 (CZTS) solar cells based on a short annealing step at temperatures as low as 350 °C using a molecular based precursor, fully avoiding highly toxic solvents and high-temperature sulfurization. We show that a simple device structure consisting of ITO/CZTS/CdS/Al and comprising an extremely thin absorber layer (∼110 nm) achieves a current density of 8.6 mA/cm(2). Over the course of 400 days under ambient conditions encapsulated devices retain close to 100% of their original efficiency. Using impedance spectroscopy and photoinduced charge carrier extraction by linearly increasing voltage (photo-CELIV), we demonstrate that reduced charge carrier mobility is one limiting parameter of low-temperature CZTS photovoltaics. These results may inform less energy demanding strategies for the production of CZTS optoelectronic layers compatible with large-scale processing techniques.

Crystallization of micelles at chemically terminated interfaces.

In aqueous solutions and for high concentrations triblock copolymers are known to aggregate. As a critical volume fraction of micelles is reached they crystallize. We report on grazing incident small angle neutron scattering as an experimental tool to investigate the crystallization of spherical polymer micelles in the immediate vicinity of a flat solid interface. We find for an attractive surface potential a face centered close packed structure with a random orientation perpendicular to the normal of the interface. For a repulsive potential crystallization is suppressed.