The use of 15N-labeled dietary proteins for determining true ileal amino acid digestibilities is limited by their rapid recycling in the endogenous secretions of pigs

We assessed the use of 15N-labeled dietary proteins as a possible tool for the determination of the true ileal amino acid (AA) digestibility in pigs. The first experiment was designed to study the dietary N excretion pattern at the ileum subsequent to the ingestion of a single 15N-labeled meal. In a second experiment, we compared ileal endogenous AA outputs and true AA digestibility estimates obtained in pigs ingesting 15N-labeled dietary proteins in a single meal vs. intravenous infusion of [15N]leucine for 10 d during the ingestion of a pea-based diet and a protein-free starch diet. The proportion of endogenous N found in the ileal digesta differed when the label was delivered orally (50%) vs. intravenously (72%) and changed with time. As a consequence, the true ileal AA digestibilities measured with labeled diets were lower. A third experiment demonstrated that this was due to the rapid recycling of labeled dietary N in endogenous moieties, because 15N was found in blood within 10 min of consuming the labeled meal, within 50 min of consumption in pancreatic enzymes, 90 min in bile and 4 h in ileal mucins. We conclude that the use of 15N-labeled meals for determination of true ileal AA digestibilities is limited by the fast recycling of dietary N in endogenous secretions following a single 15N-labeled meal. The accuracy of results will depend on meaningful estimates of AA flow during a limited period and accurate estimates of 15N in AA.     

Spatially Resolved Characterization of the Gas Propagator in Monolithic Structured Catalysts Using NMR Diffusiometry

Gas diffusivity measurements in opaque porous media were performed using nuclear magnetic resonance. An optimized pulsed‐field gradient stimulated echo method with free volume selection was used to investigate the propagator of thermally polarized methane gas within commercial monolithic catalyst supports. Since signal losses due to T₂ relaxation were minimized by using a short echo time, diffusion processes could be characterized by the measured propagator functions and effective diffusion coefficients were determined for a broad range of observation times and in different spatial directions. The study of this noninvasive characterization of gas diffusion found a clear effect of the monolith type and its pore size and coating on the effective gas diffusion coefficient and the apparent tortuosity for a given observation time.     

Multicomponent gas diffusion in nonuniform tubes

In many technical processes gas, multicomponent diffusion takes place in confinements that are rarely uniform in direction of their long axis (e.g., catalysts pores). Here, we show that in conical tubes multicomponent diffusion is hindered. This effect increases with ratio of inlet to outlet cone radius Λ, indifferent of the orientation of the tube. Based on the Maxwell–Stefan equations, predictive analytical solution for ideal multicomponent diffusion in slightly tapered ducts is developed. In two‐bulb diffusion experiments on a uniform tube, the results of Duncan and Toor (1962) were reproduced. Comparison of model and experiment shows that the solution presented here provides a reliable quantitative prediction of the temporal change of H₂, N₂, and CO₂‐concentration for both tube geometries, uniform and slightly conical. In the demonstrated case (Λ = 3.16), mass diffusion is 68% delayed. Thus, for gaseous diffusion in “real,” typically tapered pores the transport limitation is more serious than considered so far. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1404–1412, 2015     

A Prediction Method of the Behavior of Adhesively Bonded Structures under Cyclic Shear Loading Based on a Characterization of the Viscous Aspects of the Adhesive in an Assembly

The capabilities of structural bonding are more and more used. Estimating the abilities of an adhesive to endure repetitive loadings and to keep stable its mechanical properties along service life is an essential point to analyze in order to conduct fatigue assessments. The aim of this study is to develop a predictive tool for describing the fatigue behavior of an adhesive in an assembly under cyclic loadings. The approach developed analyzes the influence of viscosity on the mechanical behavior of an adhesive in an assembly based on monotonic and creep test results. Thanks to the evaluation of viscous phenomena, it is possible to predict the cyclic response of the adhesive. The experimental approach uses a unique bonded joint designed to limit the stress concentrations and with a maximum stress state in the center of the adhesive. In this paper, following the strategy developed under monotonic loading, experimental results under cyclic loading are presented for different types of loading using several load ratios and amplitudes. These results underline that the evolution of viscous deformations depends on the loading type. Under shear loading and for a ductile structural adhesive, the experimental results are well described using a viscoelastic–viscoplastic constitutive model with nonlinear viscous parameters. This model makes it possible to analyze the influence of different parameters on the mechanical response of bonded joints under cyclic shear loadings.     

Effect of N3 modifications on the affinity of spin label ç for abasic sites in duplex DNA

Noncovalent site‐directed spin labeling (NC‐SDSL) of abasic sites in duplex DNAs with the spin label ç , a cytosine analogue, is a promising approach for spin‐labeling nucleic acids for EPR spectroscopy. In an attempt to increase the affinity of ç for abasic sites, several N3 derivatives were prepared, and their binding affinities were determined by EPR spectroscopy. Most of the N3 substituents had a detrimental effect on binding. The triazole‐linked polyethylene‐glycol derivative ( 12 a ) showed a 15‐fold decrease in affinity, whereas the binding affinities of ethyl azido ( 8 b ) and hydroxyl ( 8 c ) derivatives were five‐ to sixfold lower. The spin‐labeled nucleoside Ç showed only a twofold decrease, thus binding better than 8 c , even though it contains the larger 2′‐deoxyribose substituent at N3 instead of a 2‐hydroxyethyl group. N3 derivatives that contained the basic ethyl amino ( 9 ) or ethyl guanidino ( 10 ) substituents had both higher binding affinity and solubility, attributed to their cationic charge at neutral pH. Compounds 9 and 10 are promising candidates for NC‐SDSL of nucleic acids, for distance measurements by pulsed EPR spectroscopy.     

New Biocompatible β-Phosphorylated Linear Nitrones Targeting Mitochondria: Protective Effect in Apoptotic Cells

The mitochondrion, an essential organelle involved in cellular respiration, energy production, and cell death, is the main cellular source of reactive oxygen species (ROS), including superoxide. Mitochondrial diseases resulting from uncontrolled/excess ROS generation are an emerging public health concern and there is current interest in specific mitochondriotropic probes to get information on in-situ ROS production. As such, nitrones vectorized by the triphenylphosphonium (TPP) cation have recently drawn attention despite reported cytotoxicity. Herein, we describe the synthesis of 13 low-toxic derivatives of N-benzylidene-1-diethoxyphosphoryl-1-methylethylamine N-oxide (PPN) alkyl chain-grafted to a pyridinium, triethylammonium or berberinium lipophilic cation. These nitrones showed in-vitro superoxide quenching activity and EPR/spin-trapping efficiency towards biologically relevant free radicals, including superoxide and hydroxyl radicals. Their mitochondrial penetration was confirmed by ³¹P NMR spectroscopy, and their anti-apoptotic properties were assessed in Schwann cells treated with hydrogen peroxide. Two pyridinium-substituted PPNs were identified as potentially better alternatives to TPP nitrones conjugates for studying mitochondrial oxidative damage.     

NOX removal in excess oxygen by plasma-enhanced selective catalytic reduction

In the off-gases of internal combustion engines running with oxygen excess, non-thermal plasmas (NTPs) have an oxidative potential, which results in an effective conversion of NO to NO₂. In combination with appropriate catalysts and ammonia (NH₃-SCR) or hydrocarbons (HC-SCR) as a reducing agent, this can be utilized to reduce nitric oxides (NO and NO₂) synergistically to molecular nitrogen.

The combination of SCR and cold plasma enhanced the overall reaction rate and allowed an effective removal of NO_X at low temperatures. Using NH₃ as a reducing agent, NO_X was converted to N₂ on zeolites or NH₃-SCR catalysts like V₂O₅–WO₃/TiO₂ at temperatures as low as 100–200 °C. Significant synergetic effects of plasma and catalyst treatment were observed both for NH₃ stored by ion exchange on the zeolite and for continuous NH₃ supply.

Certain modifications of Al₂O₃ and ZrO₂ have been found to be effective as catalysts in the plasma-assisted HC-SCR in oxygen excess. With an energy supply of about 30 eV/NO-molecule, 500 ppm NO was reduced by more than half at a temperature of 300 °C and a space velocity of 20 000 h⁻¹ at the catalyst. The synergistic combinations of NTP and both NH₃- and HC-SCR have been verified under real diesel engine exhaust conditions.     

Morphology of polymer blends in the melting section of co‐rotating twin screw extruders

The properties of polymer blends are largely determined by the morphological structure of the polymer combinations that are involved. In terms of extruder design, this means it is necessary to have models available for estimating the development of the morphology over the length of the screws. Since significant morphological changes are observed in the melting section, in particular, is it necessary to analyze not only the plasticizing process for binary material combinations but also the initial formation and further development of the morphology in this section of the extruder. In the framework of this study, experimental investigations were conducted into polypropylene/polyamide 6 (PP/PA6) blends with small components (by weight) of the disperse PA phase. Apart from varying the process conditions of screw speed and throughput, the viscosity ratio was also varied through the use of two different PP grades. The degree of melting and the development of the morphology over the length of the screws were determined for the individual tests. The study of blend morphology in the melting section reveals key findings that must be taken into account for modeling the initial formation and further development of the morphology. It is very clear that, on the second component, which melts at higher temperatures, a kind of melt film removal occurs at the surface of the granules as they melt. The drops of second component in the melting section, which are directly adjacent to components that have not yet fully melted in some cases, have already assumed dimensions (in the μm range) similar to those that are seen at the end of the extrusion process. This means that, in the melting section of the twin‐screw extruder, no volumes become detached from or are worn off the already‐molten granule surfaces. An evaluation of scanning electron micrographs also shows that, in the melting section of co‐rotating twin‐screw extruders, virtually all the degradation mechanisms that can essentially be distinguished, such as quasi‐steady drop breakup, folding, end pinching and decomposition through capillary instabilities, take place in parallel.     

Fullerene-based ruthenium catalysts: a novel approach for anchoring metal to carbonaceous supports. I. Structure

The influence of fullerenes and related support materials on the structural and catalytic properties of ruthenium was investigated. Catalysts based on C₆₀, raw fullerene black, extracted fullerene black, cathode deposit and graphite were prepared by an impregnation/activation procedure with Ru₃CO₁₂. The local co-ordination sphere of the resulting highly dispersed X-ray amorphous ruthenium was investigated by means of EXAFS. The dominating role of the presence of non-six-membered carbon rings on the structure and the stability of the Ru particles will be illustrated. This revised version was published online in July 2006 with corrections to the Cover Date.