In situ observation of synthesized nanoparticles in ultra-dilute aerosols via X-ray scattering

In-air epitaxy of nanostructures (Aerotaxy) has recently emerged as a viable route for fast, large-scale production. In this study, we use small-angle X-ray scattering to perform direct in-flight characterizations of the first step of this process, i.e., the engineered formation of Au and Pt aerosol nanoparticles by spark generation in a flow of N₂ gas. This represents a particular challenge for characterization because the particle density can be extremely low in controlled production. The particles produced are examined during production at operational pressures close to atmospheric conditions and exhibit a lognormal size distribution ranging from 5–100 nm. The Au and Pt particle production and detection are compared. We observe and characterize the nanoparticles at different stages of synthesis and extract the corresponding dominant physical properties, including the average particle diameter and sphericity, as influenced by particle sintering and the presence of aggregates. We observe highly sorted and sintered spherical Au nanoparticles at ultra-dilute concentrations (< 5 × 10⁵ particles/cm³) corresponding to a volume fraction below 3 × 10^–10, which is orders of magnitude below that of previously measured aerosols. We independently confirm an average particle radius of 25 nm via Guinier and Kratky plot analysis. Our study indicates that with high-intensity synchrotron beams and careful consideration of background removal, size and shape information can be obtained for extremely low particle concentrations with industrially relevant narrow size distributions.

     

Resumption of mitosis during post-thaw culture: a key parameter in selecting the right embryos for transfer

A new oxidative pathway for the degradation of caffeine(1,3,7-Trimethylxanthine, I) by a mixed culture consisting of strains belonging to the genera Klebsiella and Rhodococcus is presented. The mixed culture does not initiate degradation by N-demethylation either complete or partial, but instead carries out oxidation at the C-8 position resulting in the formation of 1,3,7-trimethyluric acid (TMU, II) which further gets degraded to 3,6,8-trimethylallantoin (TMA, III). Both TMU and TMA are hitherto not shown to be formed in the microbial system. Further degradation of TMA (III) by caffeine grown cells yields dimethylurea (VII) as one of the metabolites. Oxygen uptake studies indicated that caffeine(I) grown cells oxidized TMU(II), TMA (III), glyoxalic acid (VI), dimethylurea(VII), and monomethylurea(V), but not monomethyl and dimethyluric acids. The mixed culture does not accept theophylline(1,3-dimethylxanthine), theobromine(3,7-dimethylxanthine), and paraxanthine(1,7-dimethylxanthine) as the carbon source.     

All-optical wavelength conversion by semiconductor opticalamplifiers

Following a brief introduction to the applications for wavelength conversion and the different available conversion techniques, the paper gives an in depth analysis of cross gain and cross phase wavelength conversion in semiconductor optical amplifiers. The influence of saturation filtering on the bandwidth of the converters is explained and conditions for conversion at 20 Gb/s or more are identified. The cross gain modulation scheme shows extinction ratio degradation for conversion to longer wavelengths. This can be overcome using cross phase modulation in semiconductor optical amplifiers that are integrated into interferometric structures. The first results for monolithic integrated interferometric wavelength converters are reviewed, and the quality of the converted signals is demonstrated by transmission of 10 Gb/s converted signals over 60 km of nondispersion shifted single mode fiber     

Reduction of neuropeptide Y binding sites in the rat hippocampus after electroconvulsive stimulations

The role of vasoactive intestinal peptide (VIP) was investigated when mucosal stroking and 5-hydroxytryptamine (5-HT) were used to activate neural reflexes that stimulate chloride secretion in the guinea pig colon. Muscle-stripped segments of colon containing intact submucosal ganglia without myenteric ganglia were set up in modified flux chambers in order to record short-circuit current (Isc). Mucosal stroking with a brush for 1 s or a pulse of 5-HT (injection of 15 microliters of 100 microM 5-HT into 1.5 ml of mucosal solution) caused an increase in Isc that was reduced by the VIP antagonist, neurotensin6-11-VIP7-28, in a concentration-dependent manner. The Isc responses to mucosal stroking and a 5-HT pulse were reduced by 53% and 58%, respectively, by 2 microM neurotensin6-11-VIP7-28. The residual Isc response in the presence of neurotensin6-11-VIP7-28 was abolished by atropine. Blockade of 5-HT1P receptors on submucosal afferent neurons decreased Isc responses to stroking or a 5-HT pulse. The residual Isc response after 5-HT1P receptors were blocked was reduced by only 11-14% by neurotensin6-11-VIP7-28. In the presence of blockade of both 5-HT1P and VIP receptors, atropine abolished the Isc response to both stimuli. The observations suggest that the neural circuitry activated by stroking includes at least two independent pathways. One pathway contains VIP neurons which receive inputs directly or indirectly from 5-HT1P receptor-containing afferents. A second pathway involves muscarinic cholinergic transmission that is independent of 5-HT1P and VIP receptor activation.     

Fe calculations of stress fields from cracks located at the fusion line of weldments

This paper investigates the stress fields for a crack located at the fusion line of a weldment. The strength mis-matching and the size of the HAZ were varied, and the corresponding distribution of the maximum principal stress was examined. The weld metal strength was globally overmatched with respect to the base material, but locally over- and undermatched with respect to the heat affected zone. Three cases of mis-match were compared, and it was found that reducing the strength of the HAZ lowered the maximum principal stresses.     

A Bethe theory for the directional dependence of stopping by molecules

We derive a Bethe formula for the stopping of swift ions by target molecules oriented with respect to the beam. The theory is characterized by a directional mean excitation energy formed from transition energies and dipole matrix elements. The expression for the mean excitation energy is similar to the one for an isotropic sample but the dipole matrix elements corresponding to the various transition moment directions carry unequal weights which depend on the orientation of the molecule with respect to the beam. For a large class of molecules, the logarithm of the mean excitation energy is linear in sin² θ, where θ denotes the angle between the beam and the principal molecular axis. We illustrate the properties of the theory in the simple case of a diatomic molecule.     

A phosphorus budget of a poultry farm and a dairy farm in the southeastern U.S., and the potential impacts of diet alterations

Current and potential environmental problems associated with P transport from lands receiving high application rates of animal waste are a major concern. Phosphorus management strategies are needed to reduce P loading on land. This study was conducted to compare on-farm P budgets for a modern broiler farm and a dairy farm under traditional diets and management practices. Phosphorus inputs, recycling and outputs were assessed for both farms. A typical broiler and a dairy farmer from North Carolina were interviewed and pertinent information for the study was obtained, in cooperation with extension agents, and other professionals associated with the farms. The annual on-farm P surplus for the broiler farm was 6,380 kg, while that for the dairy farm was 1,141 kg. This corresponds to an annual application of 65 kg P ha^–1 for the broiler farm and 20 kg P ha^–1 for the dairy farm in excess of removal. The potential for reducing P surpluses by the addition of phytase enzymes and/or the use of low phytic acid corn (Zea mays L.) feed in the broiler farm diet was also assessed. Estimates by animal nutritionists indicate that feed supplementation with phytase enzyme can reduce the broiler farm's P surplus by 33%. The use of low phytic acid corn can reduce the surplus by 49% and a combination of the two can reduce the surplus by 58%. In this study, the incorporation of soybean (Glycine max (L.) Merr.) and alfalfa (Medicago sativa) land into the waste utilization plan of the dairy farm decreases the annual P surplus from 20 to 9 kg P ha^–1. The use of new feed technology and expanding waste application to a larger land base can significantly alter the P budgets of broiler and dairy farms and reduce P surpluses, minimizing the risk of environmental problems.     

The effect of synthesis gas composition on the Fischer–Tropsch synthesis over Co/γ-Al2O3 and Co–Re/γ-Al2O3 catalysts

The Fischer–Tropsch synthesis over Co/γ-Al₂O₃ and Co–Re/γ-Al₂O₃ was investigated in a fixed-bed reactor at 20 bar and 483 K using feed gases with molar H₂/CO ratios of 2.1, 1.5 and 1.0 simulating synthesis gas derived from biomass. With lower H₂/CO ratios in the feed, the CO conversion and the CH₄ selectivity decreased, while the C₅₊ selectivity and olefin/paraffin ratio for C₂–C₄ increased slightly. The water–gas shift activity was low for both catalysts, resulting in high molar usage ratios of H₂/CO (close to 2.0), even at the lower inlet ratios (i.e. 1.5 and 1.0). For both catalysts, the drop in the production rate of hydrocarbons when shifting from an inlet ratio of 2.1 to 1.5 was significant mainly because the H₂/CO usage ratio did not follow the change in the inlet ratio. The hydrocarbon selectivities were rather similar for inlet H₂/CO ratios of 2.1 and 1.5, while significantly deviating from those for an inlet ratio of 1.0. With the studied catalysts, it is possible to utilize the advantages of an inlet ratio of 1.0 (higher selectivity to C₅₊, lower selectivity to CH₄, no water–gas shifting of the bio-syngas needed prior to the FT reactor) if a low syngas conversion is accepted.     

Acid-catalysed reduction of ferrylmyoglobin: product distribution and kinetics of autoreduction and reduction by NADH

The pH dependence of iron(II)/iron(III) product distribution, following reduction of the hypervalent iron in equine ferrylmyoglobin by the protein moiety of the pigment (so-called autoreduction) and by NADH (nicotinamide adenine dinucleotide, reduced) and the rate of reduction was found to depend different on pH. Autoreduction is specific acid catalysed and has a more modest temperature dependence than autoxidation of oxymyoglobin, with the activation parameters H ^#=58.5±0.4 kJ·mol^–1 and S ^#=2.7±0.1 J·mol^–1·K^–1 in 0.16 mol·1^–1 NaCl. The product of autoreduction is the iron(III) pigment metmyoglobin, which is slightly modified in the protein moiety. The reaction has a positive kinetic salt effect from which it is deduced that the reactive centre of ferrylmyoglobin has a charge of +1 in agreement with the structure Fe(IV)=O. Reduction by NADH involves parallel reactions of two pigment forms in acid/base equilibrium with each other with a pK _a equal to 4.9, both forms yielding metmyoglobin as well as the iron(II) pigment, oxymyoglobin, as products. The protonated form reacts faster than the deprotonated form, and two-electron transfer has greater importance for the protonated form with a limiting Fe(II)/Fe(III) product ratio of 0.6 in acidic solution compared to 0.12 in alkaline solution. A square root dependence of rate on NADH concentration suggests involvement of NAD·radicals with a disproportionation as the termination reaction.

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Säure-katalysierte Reduktion von Ferrylmyoglobin. Produktdistribution und Kinetik der Autoreduktion und Reduktion von NADH

Zusammenfassung Die Reaktionsgeschwindigkeit und das Eisen(II)/Eisen(III)-Verhältnis des Produkts nach Reduktion von hypervalentem Eisen in Ferrylmyoglobin aus Pferden zeigt eine unterschiedliche pH-Abhängigkeit der sogenannten Autoreduktion (Reduktion am Proteinteil des Pigments) sowie der Reduktion durch NADH. Die Autoreduktion weist eine spezifische Säure-Katalyse auf sowie eine moderate Temperaturabhängigkeit im Vergleich zur Autooxidation von Oxymyoglobin mit den Aktivierungsparametern H ^#=58.5±0.4 kJ·mol^–1 und S ^#=2.7±0.1 J·mol^–1·K^–1 in 0.16 mol·1^–1 NaCl. Das Produkt der Autoreduktion ist das Eisen(III)-Pigment Metmyoglobin mit leicht modifiziertem Proteinanteil. Die Reaktion hat einen positiv kinetischen Salzeffekt, woraus zu erschließen ist, daß das reaktive Zentrum im Ferrylmyoglobin die Ladung +1 übereinstimmend mit der Struktur Fe(IV)=O besitzt. Die Reduktion durch NADH weist auf parallele Reaktionen von zwei Pigmentformen in einem Säure/Base-Gleichgewicht mit pk _a=4.9 hin, beide Formen ergeben Metmyoglobin sowie das Eisen(II)-Pigment Oxymyoglobin als Produkt. Die protonisierte Form reagiert schneller als die deprotonisierte Form, und eine zwei-Elektronenübertragung hat größere Bedeutung für die protonisierte Form mit einem Fe(II)/Fe(III) Produktverbrauch von 0.6 in der Säurelösung und 0.12 in der Baselösung. Die Quadratwurzel Abhängigkeit der Geschwindigkeit von NADH deutet auf eine Teilnahme von NAD-Radikalen mit Disproportionierung als Schlußreaktion.