Attentional sensitization of unconscious cognition: Task sets modulate subsequent masked semantic priming.

According to classical theories, automatic processes are autonomous and independent of higher level cognitive influence. In contrast, the authors propose that automatic processing depends on attentional sensitization of task-congruent processing pathways. In 3 experiments, the authors tested this hypothesis with a modified masked semantic priming paradigm during a lexical decision task by measuring event-related potentials (ERPs): Before masked prime presentation, participants attended an induction task either to semantic or perceptual stimulus features designed to activate a semantic or perceptual task set, respectively. Semantic priming effects on the N400 ERP component, an electrophysiological index of semantic processing, were obtained when a semantic task set was induced immediately before subliminal prime presentation, whereas a previously induced perceptual task set attenuated N400 priming. Across experiments, comparable results were obtained regardless of the difficulty level and the verbal or nonverbal nature of the induction tasks. In line with the proposed attentional sensitization model, unconscious semantic processing is enhanced by a semantic and attenuated by a perceptual task set. Hence, automatic processing of unconscious stimuli is susceptible to top-down control for optimizing goal-related information processing. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Computational spectroscopy and reaction dynamics

Physico- and bio-chemical processes on the femto- to picosecond time scale are ideally suited to be investigated with all-atom simulations. They include, amongst others, vibrational relaxation, ligand migration in sterically demanding environments (proteins, ices), or vibrational spectra. By comparing with experimental data, the results can be used to obtain an understanding of the mechanisms underlying the observations. Furthermore, most of these processes are sensitive to the intermolecular interactions. Therefore, detailed refinement of such interaction potentials is possible.     

GC/EI-MS Determination of the Diastereomer Distribution of Phytanic Acid in Food Samples

Phytanic acid (3,7,11,15-tetramethylhexadecanoic acid) is a branched-chain fatty acid, produced by bacteria by means of oxidation and biohydrogenation of the chlorophyll side chain phytol (3,7R,11R,15-tetramethylhexadec-2-en-1-ol). The later reaction generates to a new stereogenic center on C-3 which can be both 3R- or 3S-configured. Thus, two diastereomers (3S,7R,11R,15- and 3R,7R,11R,15-phytanic acid) are naturally produced. In this study we examined the diastereomer composition of phytanic acid in terrestrial and marine food samples. Phytanic acid was transferred into its methyl ester which was analyzed by GC/MS in the selected ion monitoring mode. The first eluted diastereomer in the samples was tentatively identified as 3S,7R,11R,15-phytanic acid. The marine samples were clearly dominated by 3S,7R,11R,15-phytanic acid whose abundance was higher in marine mammals than in fish. Milk from one organic cow collected over a period of 30 days showed lower proportions of 3S,7R,11R,15-phytanic acid than milk from one cow raised with conventional feed. The difference between organic and conventional dairy products (cheese and butter) was not as pronounced as in milk. Milk samples from other mammals (goat, sheep, mare, camel, moose, and human) also showed an excess of 3S,7R,11R,15-phytanic acid except for camel and moose milk.     

Polymer-assisted formation of hydrophobized,shape-anisotropic zinc oxide nanoparticles via an inverse emulsion technique

A one-step inverse emulsion process using amphiphilic surface-active copolymers for the synthesis of hydrophobized, shape-anisotropic inorganic nanoparticles is presented. While such structures are normally prepared sequentially by particle formation and hydrophobization, we have combined both reactions. This approach is demonstrated exemplarily with zinc oxide (ZnO) nanoparticles. A key issue is the design of amphiphilic copolymers that act as emulsifiers to enable an aggregate-free redispersion of the particles and to stabilize the inverse emulsion for the precipitation in the droplets. In a first approach, the stabilizing as well as the hydrophobizing property of the copolymers are combined with the ability to control the crystallization in one polymer (structure-directing emulsifier—SDE). In a second approach, a mixture of two polymers is applied: an amphiphilic copolymer for hydrophobizing/stabilizing the inorganic nanoparticles and a polar or double hydrophilic polymer that induces the anisotropic growth of the ZnO nanocrystals (structure-directing agents—SDA). Homopolymers and block copolymers, consisting of phosphonic acid groups or propylene oxide groups, were used as SDAs. Typically, hydrophobized shape-anisotropic particles of up to 600 nm in length and with an aspect ratio of 1:4 were obtained.     

Labortest zur Minimierung des Versuchsaufwandes bei Pilotfiltrationen

Investigating beer filtration using cellulose fibers requires appropriate methods. One aspect is the preparation of large scale trials. Starting from the filterability test according to Raible and based on the results of diverse pilot scale trials, a laboratory test was created. Apparatus, procedure and methods of assessing the results are described. The new test is qualified for reducing time and effort in upper scale trials, especially in case of varying filter aids compositions.     

The inverse problem in granulation modeling—Two different statistical approaches

This article is concerned with parameter estimation for a multidimensional population balance model for granulation. Experimental results were obtained by running a laboratory mixer with sodium carbonate and aqueous polyethylene glycol solutions. Subsequently, a prescan of suitable parameter combinations utilising the experimental results is performed, and a local surrogate model constructed around the best combination. For the actual estimation of the parameters and their uncertainties two different approaches are applied—a projection method and a Bayesian approach. It is found that the model predictions with the parameters obtained through both methods are similar. Furthermore, the uncertainties in the model predictions increase as the experimental uncertainties are increased. Studies of the marginal densities of two‐parameter combinations obtained through the Bayesian approach show a correlation between the collision and breakage rate constant, giving potential hints for further model development. Furthermore, a bimodal distribution of the compaction rate constant is observed. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Experimental and numerical investigation of supported rhodium catalysts for partial oxidation of methane in exhaust gas diluted reaction mixtures

The partial oxidation of methane/oxygen mixtures with large exhaust gas dilution (46.3 vol% H₂O and 23.1 vol% CO₂) has been investigated experimentally and numerically over Rh/CeO₂-ZrO₂, Rh/ZrO₂ and Rh/α-Al₂O₃ catalysts. Experiments were carried out in a short-contact-time reactor at 5 bar and included exhaust gas analysis, temperature measurements along the reactor, and catalyst characterization. Additional experiments were performed in an optically accessible channel-flow reactor and involved in situ Raman measurements of major gas-phase species concentrations over the catalyst boundary layer and laser-induced fluorescence (LIF) of formaldehyde. A full elliptic two-dimensional numerical code that included elementary hetero-/homogeneous chemical reaction schemes and relevant heat transfer mechanisms in the solid was used in the simulations. The employed heterogeneous reaction mechanism, including only active Rh sites, reproduced the experiments with good accuracy. The ratio of active to geometrical surface area, deduced from hydrogen chemisorption measurements, was the single model parameter needed to account for the effect of different supports. This indicated that water activation occurring on support sites, resulting in inverse OH spillover from the support to the noble metal sites, could be neglected under the present conditions with high water dilution. An evident relationship between noble metal dispersion and catalytic behavior, in terms of methane conversion and synthesis gas yields, could be established. Both measurements and predictions indicated that an increasing Rh dispersion (in the order Rh/α-Al₂O₃, Rh/ZrO₂, and Rh/CeO₂-ZrO₂) resulted in higher methane conversions, lower surface temperatures, and higher synthesis gas yields.     

Generation and characterization of a novel recombinant antibody against 15-ketocholestane isolated by phage-display

The employment of monoclonal antibodies (Mabs) to identify disease-associated biomarkers in clinical samples represents the underlying principle for many diagnostic tests. To date, these have been principally developed for protein targets with few reported applications for lipids due to their hydrophobicity and poor immunogenicity. Oxysterols represent a family of lipids implicated in diverse human diseases where Mab-based detection assays could have a profound effect on their utility as clinical biomarkers. These are usually identified in patients' samples by mass- spectrometry based approaches. Here, we describe an antibody phage-library based screening methodology for generating a recombinant monoclonal antibody (RAb) targeting the oxysterol-15-ketocholestane (15-KA), a lipid implicated in multiple sclerosis and Autoimmune Encephalomyelitis (EAE). The antibody is highly specific for 15-KA and shows little or no binding activity for other closely related oxysterols. We employ RAb2E9 to address the controversy over whether 15-KA is a true biomarker for MS/EAE and show that 15-KA is undetectable in serum taken from mice with EAE using antibody based detection methodologies; a finding confirmed by mass-spectrometry analysis. This study demonstrates the technical feasibility of using phage display to isolate highly specific antibodies against poorly immunogenic, small molecule lipids.     

Thermal Stability, Phase Evolution, and Crystallization in Si-B-C-N Ceramics Derived from a Polyborosilazane Precursor

Amorphous Si-B-C-N ceramic powder samples obtained by thermolysis of boron-modified polysilazane, {B[C₂H₄Si(H)NH]₃} _n , were isothermally annealed at different temperatures (1400–1800°C) and hold times (3, 10, 30, and 100 h). A qualitative and semiquantitative analysis of the crystallization behavior of the materials was performed using X-ray diffraction (XRD). The phase evolution was additionally followed by ¹¹B and ²⁹Si MAS NMR as well as by FT-IR spectroscopy in transmission and diffuse reflection (DRIFTS) modes. Bulk chemical analyses of selected samples were performed to determine changes in the chemistry/phase composition of the materials. It was observed that silicon carbide is the first phase to nucleate around 1400–1500°C, whereas silicon nitride nucleates at and above 1700°C. Crystallization accelerates with increasing annealing temperature and proceeds with increasing annealing time. Furthermore, the surface area of the powders strongly influences the thermal stability of silicon nitride and thus controls overall chemical and phase composition of the materials on thermal treatment.