Infrared characterization of the surface intermediates in the oxidation of toluene on vanadyl pyrophosphate catalysts

The adsorption and reaction of toluene on vanadyl pyrophosphate catalysts was studied by in situ infrared spectroscopy. Strongly adsorbed benzaldehyde and physically adsorbed cyclic anhydride species were observed at temperatures above 523 K. Water formed during reaction generates acid hydroxyl groups which cause a stronger adsorption of benzaldehyde and consecutive oxidation reactions. By co-adsorption of pyridine the acid sites are blocked and the deeper oxidation is suppressed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cross-Sectional Associations of Food Consumption with Plasma Fatty Acid Composition and Estimated Desaturase Activities in Finnish Children

Plasma fatty acid (FA) composition is known to be an indicator of dietary fat quality, but the associations of other dietary factors with plasma FA composition remain unknown in children. We investigated the cross-sectional associations of food consumption with the proportions of FA and estimated desaturase activities in plasma cholesteryl esters (CE) and phospholipids (PL) among children. The subjects were a population sample of 423 children aged 6–8 years examined at baseline of The Physical Activity and Nutrition in Children (PANIC) Study. We assessed food consumption by food records and plasma FA composition by gas chromatography. We used linear regression models adjusted for age, sex, physical activity and total energy intake to analyze the associations. A higher consumption of vegetable oil-based margarine (fat 60–80 %) was associated with a higher proportion of linoleic and α-linolenic acids in plasma CE and PL. A higher consumption of high-fiber grain products was related to a lower proportion of oleic acid in CE and PL. The consumption of candy was directly associated with the proportion of palmitoleic and oleic acid in plasma CE. The consumption of vegetable oil-based margarine was inversely associated with estimated stearoyl-CoA-desaturase activity in plasma CE and PL and the consumption of candy was directly related to it in plasma CE. The results of our study suggest that plasma FA composition is not only a biomarker for dietary fat quality but also reflects the consumption of high-fiber grain products and foods high in sugar among children.     

Tracking Hidden Binding Pockets Along the Molecular Recognition Path of l-Trp to Indoleamine 2,3-Dioxygenase 1

Indoleamine 2,3-dioxygenase 1 (IDO1) catalyzes the oxidative cleavage of l -Tryptophan (l -Trp) to yield N-formyl-kynurenine in the first and rate limiting step of the kynurenine pathway. Bioactive metabolites, involved in the regulation of important immunological responses and neurological processes, are then produced by downstream enzymes along the pathway. Inhibitors of IDO1 are being designed and developed as therapeutic agents for immuno-oncology. In this work, we investigated the molecular recognition path of l -Trp to IDO1, integrating biophysical methods with supervised molecular dynamics (suMD) and mutagenesis experiments. Results allowed disclosing for the first time high and low dissociation constants of l -Trp to IDO1, and the presence of a metastable interaction site located at the upper part of a channel whose borders are defined by the EF-loop and the C-terminal part of the JK-loop. Collectively, our results provide new clues for the design of next-generation IDO1 ligands.     

Catalytic Reduction of 4-Nitrobenzoic Acid by cis-[Rh(CO)2(Amine)2](PF6) Complexes Under Water–Gas Shift Reaction Conditions: Kinetics Study

Rhodium(I) complexes of the type, cis-[Rh(CO)₂(amine)₂](PF₆) where (amine = 3-picoline, 2-picoline, pyridine, 2,6-lutidina or 3,5-lutidine) dissolved in 80% aqueous amine solutions catalyzed the selective reduction of 4-nitrobenzoic acid to 4-aminobenzoic acid under CO atmosphere. The importance of these catalytic systems is their high chemo selectivity for the aromatic nitro group of the 4-nitrobenzoic acid with respect to the carboxylic group, allowing the production of the desired aromatic amine in high yields. The 4-aminobenzoic acid production depends on the nature of the coordinated amine. The Rh/3,5-lutidine system, the most active catalyst among tested, displays turnover frequencies for 4-aminobenzoic acid production of about 173 moles per mole Rh per day for [Rh] = 1 × 10^?4 mol, [4-nitrobenzoic acid] = 3.82 × 10^?3mol, 10 mL of 80% aqueous 3,5-lutidine, P(CO) = 0.9 atm at 100 °C. Analyses of kinetic results for the Rh/3,5-lutidine system show a first order dependence on 4-nitrobenzoic acid concentration, a non-linear dependence on CO pressure, a segmented Arrhenius plot and dependence on the nature of the reducing gas agent. These data are discussed in terms of a possible mechanism.     

Linking Simultaneous In Situ WAXS/SAXS/Raman with Raman/ATR/UV–vis Spectroscopy: Comprehensive Insight into the Synthesis of Molybdate Catalyst Precursors

A new setup is presented which enables simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) and Raman spectroscopic experiments during the synthesis of Mo-based mixed oxide catalyst precursors at the μ-spot beamline at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung (BESSY). Furthermore, we report about the separate monitoring of the same reactions under comparable conditions by simultaneous combined ATR/UV–vis/Raman spectroscopic measurements. For testing the performance of both experimental setups two syntheses were described comprising the precipitation of metal molybdates by mixing solutions of metal nitrates and ammonium heptamolybdate. Additionally, the effect of H₃PO₄ admixture on precipitation was investigated. The combined evaluation of spectroscopic and WAXS/SAXS data allows the discrimination between different molybdate species appearing in solution and precipitate. Furthermore, these molybdate species could be assigned to separate phases of different crystallinity.     

Invariants, Patterns and Weights for Ordering Terms

We prove that any simplification order over arbitrary terms is an extension of an order by weight, by considering a related monadic term algebra called the spine. We show that any total ground-stable simplification order on the spine lifts to an order on the full term algebra. Conversely, under certain restrictions, a simplification ordering on the term algebra defines a weight function on the spine, which in turn can be lifted to a weight order on the original ground terms which contains the original order. We investigate the Knuth–Bendix and polynomial orders in this light. We provide a general framework for ordering terms by counting embedded patterns, which gives rise to many new orderings. We examine the recursive path order in this context.     

Multiphase microstructure in steel bars produced by dieless drawing

In the dieless drawing technology the drawing dies are replaced by a heating device, generally by an induction coil. Bars of different cross-sections, round or even rectangular, with varying dimensions along the length can be produced. By using a cooling box in connection with the heating device this deformation process may also be employed for a thermomechanical treatment of steels. The special cooling strategy with low cooling rates at high temperatures (during ferrite formation) and higher cooling rates at lower temperatures favours the formation of multiphase microstructures (ferrite - bainite/martensite) with a low yield strength but a strong work hardening effect. The experiments were carried out on rods with a diameter of 16 mm of a plain low carbon steel (0.1%C, 0.7%Mn). The specimens were locally heated up to the maximum temperature ?_max that initiates the dieless drawing process, and subsequently cooled with different coolants. The change in yield strength and tensile strength and the corresponding change in the ratio of both could be achieved by variation of ?_max and the cooling conditions. The multiphase microstructure with desired mechanical properties was produced at a strain of about more than 0.45 within the region of ?_max ≈ 900–1000°C and a finale cooling rate of about 20 K/s.