Buoyancy induced limits for nanoparticle synthesis experiments in horizontal premixed low-pressure flat-flame reactors

Premixed low-pressure flat-flame reactors can be used to investigate the synthesis of nanoparticles. The present work examines the flow field inside such a reactor during the formation of carbon (soot) and iron oxide (from Fe(CO)₅) nanoparticles, and how it affects the measurements of nanoparticle size distribution. The symmetry of the flow and the impact of buoyancy were analysed by three-dimensional simulations and the nanoparticle size distribution was obtained by particle mass spectrometry (PMS) via molecular beam sampling at different distances from the burner. The PMS measurements showed a striking, sudden increase in particle size at a critical distance from the burner, which could be explained by the flow field predicted in the simulations. The simulation results illustrate different fluid mechanical phenomena which have caused this sudden rise in the measured particle growth. Up to the critical distance, buoyancy does not affect the flow, and an (almost) linear growth is observed in the PMS experiments. Downstream of this critical distance, buoyancy deflects the hot gas stream and leads to an asymmetric flow field with strong recirculation. These recirculation zones increase the particle residence time, inducing very large particle sizes as measured by PMS. This deviation from the assumed symmetric, one-dimensional flow field prevents the correct interpretation of the PMS results. To overcome this problem, modifications to the reactor were investigated; their suitability to reduce the flow asymmetry was analysed. Furthermore, ‘safe’ operating conditions were identified for which accurate measurements are feasible in premixed low-pressure flat-flame reactors that are transferrable to other experiments in this type of reactor. The present work supports experimentalists to find the best setup and operating conditions for their purpose.     

Catalytic behavior of nickel nanoparticles: gasborne vs. supported state

To study the pure catalytic activity of metallic nanoparticles, the formation of methane on gasborne Ni nanoparticles, so called aerosol catalysis experiments, were performed. Beside effects typical for the methanation such as poisoning of the particle surface at temperatures above 385°C, the maximum of the catalytic activity was observed for Ni particles of about 14 nm, i.e. in a size range, which is quite uncommon for typical nanoeffects of metallic particles. To clarify, which catalytic phenomena are related to the aerosol state, the same reaction was performed on supported Ni nanoparticles, which were also generated and conditioned in the gas phase and deposited on a SiO₂ surface by thermophoresis. For these supported particles, the same reaction conditions were established as before for the gasborne Ni nanoparticles. However, differences in the mass transport characteristics of educt and product molecules to the particles were encountered and led to lower overall reaction rates. While qualitatively poisoning kinetics and activation energies agreed for both cases, significant differences were observed for the size dependence of the catalytic activity and for the sintering kinetics. The observed shift of the optimum size for the methanation from 14 nm (aerosol) to 25 nm (on support) can be explained by different adsorption enthalpies of the educt gases on aerosol and supported Ni nanoparticles, respectively.     

In‐Situ Determination of the Charging of Nanometer and Submicron Particles at High Temperatures

Thermal charging of submicron and nanometer particles has been studied for model aerosols of TiO₂ and SiO₂ as well as Al‐Si (aluminosilicate) at 1 000 °C with a new quasi in‐situ technique. The size dependence of the particle separation efficiency for electrostatic precipitation was determined. The charging state of the particles was obtained from evaluating the global Deutsch number for precipitation in an electric field applied to a laminar flow based on particle trajectory considerations.     

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol^?1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg^?1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.     

<Emphasis Type="Italic">In-situ</Emphasis><Superscript>57</Superscript>Fe Mössbauer characterization of iron oxides in pigments of a rupestrian painting from the Serra da Capivara National Park,in Brazil,with the backscattering Mössbauer spectrometer MIMOS II

It is reported the use of the miniaturized portable ⁵⁷Fe Mössbauer backscattering spectrometer MIMOS II to perform in situ measurements in the archaeological site known as Toca do Boqueirão do Sítio da Pedra Furada (BPF), in Serra da Capivara National Park, in order to specifically examine shades of dark red pigments and compare their differences relatively to the light red part of the same painting. The hyperfine Mössbauer parameters reveal that the dark red area of the rupestrian painting is composed of three populations of hematite and of a small proportion of maghemite, whereas the light red are of the same painting contain hematite mixed with a small proportion of maghemite and a (super)paramagnetic Fe ³⁺. The Fe content in the dark red area from the rupestrian painting is of approximately twice the amount in the light red of the same prehistoric graphism. The corresponding analysis of red ochre sample collected in the excavation of these archaeological site exhibited two populations of hematite and also a small proportion of maghemite.     

A mass filter based on an accelerating traveling wave

We describe a novel mass filtering concept based on the acceleration of a pulsed ion beam through a stack of electrostatic plates. A precisely controlled traveling wave generated within such an ion guide will induce a mass-selective ion acceleration, with mass separation ultimately accomplished via a simple energy-filtering system. Crucial for successful filtering is that the velocity with which the traveling wave passes through the ion guide must be dynamically controlled in order to accommodate the acceleration of the target ion species. Mass selection is determined by the velocity and acceleration with which the wave traverses the ion guide, whereby the target species will acquire a higher kinetic energy than all other lighter as well as heaver species. Finite element simulations of this design demonstrate that for small masses a mass resolution M/DeltaM approximately 1000 can be achieved within an electrode stack containing as few as 20 plates. Some of the possible advantages and drawbacks which distinguish this concept from established mass spectrometric technologies are discussed.     

Direct entry to peptidyl ketones via SmI2-mediated C-C bond formation with readily accessible N-peptidyl oxazolidinones

In this work, a new method for the preparation of peptidyl ketones is presented employing a SmI(2)/H(2)O-mediated coupling of N-peptidyl oxazolidinones with electron-deficient alkenes. The requisite peptide imides were easily prepared by solution-phase peptide synthesis starting from an N-acyl oxazolidinone derivative of an amino acid. Importantly, they could be used directly in the C-C bond-forming step without the need for further functionalization. Coupling of these peptide derivatives with a second peptide possessing an N-terminal acryloyl group leads to ketomethylene isosteres of glycine-containing peptides. This method represents an alternative means for ligating two small peptides through a C-C bond-forming step.     

Pharmacological characterization of ligands at recombinant NMDA receptor subtypes by electrophysiological recordings and intracellular calcium measurements

Generation of in vitro cellular assays using fluorescence measurements at heterologously expressed NMDA receptors would speed up the process of ligand characterization and enable high-throughput screening. The major drawback to the development of such assays is the cytotoxicity caused by Ca(2+)-flux into the cell via NMDA receptors upon prolonged activation by agonists present in the culture medium. In the present study, we established four cell lines with stable expression of NMDA receptor subtypes NR1/NR2A, NR1/NR2B, NR1/NR2C, or NR1/NR2D in BHK-21 cells. To assess the usefulness of the stable cell lines in conjunction with intracellular calcium ([Ca(2+)](i)) measurements for evaluation of NMDA receptor pharmacology, several ligands were characterized using this method. The results were compared to parallel data obtained by electrophysiological recordings at NMDA receptors expressed in Xenopus oocytes. This comparison showed that agonist potencies determined by [Ca(2+)](i) measurements and electrophysiological recordings correlated well, meaning that the stable cell lines in conjunction with [Ca(2+)](i) measurements provide a useful tool for characterization of NMDA receptor ligands. The agonist series of conformationally constrained glutamate analogues (2S,3R,4S)-alpha-(carboxycyclopropyl)glycine (CCG), 1-aminocyclobutane-r-1,cis-3-dicarboxylic acid (trans-ACBD), and (+/-)-1-aminocyclopentane-r-1,cis-3-dicarboxylic acid (cis-ACPD), as well as the highly potent agonist tetrazolylglycine were among the characterized ligands that were assessed with respect to subtype selectivity at NMDA receptors. However, none of the characterized agonists displays more than 2-3 fold selectivity towards a specific NMDA receptor subtype. Thus, the present study provides a broad pharmacological characterization of structurally diverse ligands at recombinant NMDA receptor subtypes.     

Formation and thickness evolution of periodic twin domains in manganite films grown on SrTiO3(001) substrates

We present an extended synchrotron x-ray scattering study of the structure of thin manganite films grown on SrTiO3(001) substrates and reveal a new kind of misfit strain relaxation process which exploits twinning to adjust lattice mismatch. We show that this relaxation mechanism emerges in thin films as one-dimensional twinning waves which freeze out into a twin domain pattern as the manganite film continues to grow. A quantitative microscopic model which uses a matrix formalism is able to reproduce all x-ray features and provides a detailed insight into this novel relaxation mechanism. We further demonstrate how this twin angle pattern affects the transport properties in these functional films.